Showing papers by "J. Fraser Stoddart published in 2009"

Noncovalent Functionalization of Single-Walled Carbon Nanotubes

Abstract: Single-walled carbon nanotubes (SWNTs) have attracted much attention on account of their potential to be transformed into new materials that can be employed to address a wide range of applications. The insolubility of the SWNTs in most solvents and the difficulties of handling these highly intractable carbon nanostructures, however, are restricting their real-life applications at the present time. To improve upon the properties of the SWNTs, low-cost and industrially feasible approaches to their modifications are constantly being sought by chemists and materials scientists. Together, they have shown that noncovalent functionalization of the SWNTs can do much to preserve the desired properties of the SWNTs while remarkably improving their solubilities. This Account describes recent advances in the design, synthesis, and characterization of SWNT hybrids and evaluates applications of these new hybrid materials based on noncovalently functionalized SWNTs. Their solubilization enables the characterization of t...

The chemistry of the mechanical bond

Abstract: The use of templation in the synthesis of unnatural products where two or more components are mechanically interlocked has not only raised the efficiency of their production to near quantitative levels in some instances, but the molecular recognition that aids and abets the templation is also part and parcel of the molecules after they have been prepared, purified and presented for investigation. The fact that the molecular recognition ‘lives on’ in mechanically interlocked molecules, following their templated formation, makes them prime candidates for applications that straddle the scientific and technical worlds from devices that could spawn new information technologies to integrated systems that could have fundamental applications in the health-care industries. The challenge to make more and more sophisticated compounds is predicated upon our fundamental understanding of the nature of the mechanical bond and how this associated knowledge base can be employed to do complex systems chemistry in very different environments where emergent phenomena become the order of the day (critical review, 104 references).

Light-Operated Mechanized Nanoparticles

Abstract: Mesoporous silica (MCM-41) nanoparticles modified by azobenzene derivatives, capable of storing small molecules and releasing them following light irradiation, have been fabricated and characterized. In the presence of the β-cyclodextrin and/or pyrene-modified β-cyclodextrin rings, the β-cyclodextrin and/or pyrene-modified β-cyclodextrin rings will thread onto the azobenzene-containing stalks and bind to trans-azobenzene units to form the pseudorotaxanes, thus sealing the nanopores and stopping release of the cargo. Upon irradiation, the isomerization of trans-to-cis azobenzene units leads to the dissociation of the β-cyclodextrin and/or pyrene-modified β-cyclodextrin rings from the stalks, thus opening the gates to the nanopores and releasing the cargo.

Mechanised nanoparticles for drug delivery

Abstract: Time and time again humanity is faced with a unifying global crisis that crosses the many great divides in different societies and serves to bring once segregated communities back together as a collective whole. This global community instinctively turns to science to develop the means of addressing its most pressing problems. More often than not, these forces dictate the direction that scientific research takes. This influence is no more apparent than in the field of supramolecular chemistry where, for decades now, its responsibility to tackle such issues has been put on the back burner as a consequence of a lack of platforms with which to deliver this contemporary brand of chemistry to meaningful applications. However, the tide is slowly turning as new materials emerge from the field of nanotechnology that are poised to host the many attractive attributes that are inherent in the chemistry of these supermolecules and also in the mechanostereochemistry of mechanically interlocked molecules (MIMs), which can be reused as a sequel to supramolecular chemistry. Mesoporous silica nanoparticles (SNPs) have proven to be supremely effective solid supports as their surfaces are easily functionalised with either supermolecules or MIMs. In turn, the blending of supramolecular chemistry and mechanostereochemistry with mesoporous SNPs has led to a new class of materials – namely, mechanised SNPs that are effectively biological nanoscale ‘bombs’ that have the potential to infiltrate cells and then, upon the pulling of a chemical trigger, explode! The development of these materials has been driven by the need to devise new therapies for the treatment of cancer. Recent progress in research promises not only to control the acuteness of this widespread and insidious disease, but also to make the harsh treatment less debilitating to patients. This global scourge is the unifying force that has brought together supramolecular chemistry, mechanostereochemistry and nanotechnology, uniting these three communities for the common good. At the nanoscale level, the mechanism for the release of cargos from the confines of the nanopores in the SNPs is accomplished by way of mechanical modifications made on the surface of these functionalised supports. These mechanical motions rely on both supramolecular, i.e., host–guest complexes, and mechanostereochemical phenomena (e.g., bistable rotaxanes), which are often stimulated by changes in pH, light and redox potentials, in addition to enzymatic catalysis. The future of this field lies in the development of ‘smart bombs’ wherein the loaded mechanised SNPs are endocytosed selectively by cancer cells, whereupon an intracellular trigger causes release of a cytotoxin, effectively leading to apoptosis. This review serves to highlight (1) the evolution of surface-functionalisation of SNPs with supermolecules and also with MIMs, (2) the mechanisms through which controlled-release of cargo from mechanised SNPs occurs, and (3) results from the in vitro application of these mechanised SNPs.

Docking in metal-organic frameworks.

Abstract: The use of metal-organic frameworks (MOFs) so far has largely relied on nonspecific binding interactions to host small molecular guests. We used long organic struts (approximately 2 nanometers) incorporating 34- and 36-membered macrocyclic polyethers as recognition modules in the construction of several crystalline primitive cubic frameworks that engage in specific binding in a way not observed in passive, open reticulated geometries. MOF-1001 is capable of docking paraquat dication (PQT2+) guests within the macrocycles in a stereoelectronically controlled fashion. This act of specific complexation yields quantitatively the corresponding MOF-1001 pseudorotaxanes, as confirmed by x-ray diffraction and by solid- and solution-state nuclear magnetic resonance spectroscopic studies performed on MOF-1001, its pseudorotaxanes, and their molecular strut precursors. A control experiment involving the attempted inclusion of PQT2+ inside a framework (MOF-177) devoid of polyether struts showed negligible uptake of PQT2+, indicating the importance of the macrocyclic polyether in PQT2+ docking.

pH clock-operated mechanized nanoparticles.

Abstract: Mechanized nanoparticles (MNPs) consisting of supramolecular machines attached to the surface of mesoporous silica nanoparticles are designed to release encapsulated guest molecules controllably under pH activation. The molecular machines are comprised of cucurbit[6]uril (CB[6]) rings that encircle tethered trisammonium stalks and can be tuned to respond under specific pH conditions through chemical modification of the stalks. Luminescence spectroscopy demonstrates that the MNPs are able to contain guest molecules within nanopores at neutral pH levels and then release them once the pH is lowered or raised.

Azobenzene-based light-responsive hydrogel system.

Abstract: A deoxycholic acid-modified β-cyclodextrin derivative (2) and an azobenzene-branched poly(acrylic acid) copolymer (3) were prepared, and the association and dissociation of 2 with the trans/cis-azobenzene units in 3 were characterized by UV/vis spectroscopy, induced circular dichroism, and 1H NMR spectroscopy. The experimental results indicate that the trans-azobenzene units are bound strongly within the cavities of 2 whereas the cis-azobenzene is not bound at all. A supramolecular inclusion complex (1), formed by 2 and 3, is accompanied by the formation of a hydrogel. The light-responsive gel-to-sol and sol-to-gel phase transitions of the hydrogel, induced by trans-cis photoisomerization of the azobenzene units, were investigated. In the hydrogel system, the trans-azobenzene units in 3 are included inside the hydrophobic cavity of 2. Upon photoirradiation with UV light of 355 nm, the hydrogel is converted efficiently to the sol phase because the trans-azobenzene units are converted photochemically to the...

Dual-controlled nanoparticles exhibiting AND logic.

Abstract: Dual-controlled nanoparticles (DCNPs) are synthesized by attaching two different types of molecular machines, light-responsive nanoimpellers and pH-responsive nanovalves, to different regions of mesoporous silica nanoparticles. Nanoimpellers are based on azobenzene derivatives that are tethered to the nanopore interiors, while nanovalves are based on [2]pseudorotaxanes that are tethered to the nanoparticle surfaces. The different molecular machines operate through separate mechanisms to control the release of guest molecules that are loaded into the nanopores. When used in conjunction with one another, a sophisticated controllable release system behaving as an AND logic gate is obtained.

Controlled-access hollow mechanized silica nanocontainers.

Abstract: A new category of mechanized nanoparticles, consisting of a hollow mesoporous silica spherical framework controlled by a supramolecular system containing the alpha-cyclodextrin (alpha-CD) ring on a stalk that is tethered to the pore openings on the nanosphere, is synthesized and tested. Construction of the nanovalve relies on the hydrogen-bonding interaction between alpha-CD and the stalk. The stalk is bonded to the nanoparticle chemically and contains an anilino group that is located on the end of the linker molecule that is closest to the pore entrance. When the alpha-CD ring is complexed with the stalk at neutral pH, the bulky cyclic component is located near the pore openings, thereby blocking departure of cargo molecules that were loaded in the nanopores and hollow interior of the particle. Protonation of the nitrogen atoms at lower pH causes the binding affinity to decrease, releasing the alpha-CD and allowing the cargo molecules to escape. The properties of this newly designed pH-responsive nanovalve are compared to those of conventional mesoporous silica nanoparticles. The on-command pH-activated release is measured using luminescence spectroscopy. The effect of different stalk lengths and pH conditions on the release of fluorescent dye cargo molecules is measured.

A Mechanical Actuator Driven Electrochemically by Artificial Molecular Muscles

Abstract: A microcantilever, coated with a monolayer of redox-controllable, bistable [3]rotaxane molecules (artificial molecular muscles), undergoes reversible deflections when subjected to alternating oxidizing and reducing electrochemical potentials. The microcantilever devices were prepared by precoating one surface with a gold film and allowing the palindromic [3]rotaxane molecules to adsorb selectively onto one side of the microcantilevers, utilizing thiol-gold chemistry. An electrochemical cell was employed in the experiments, and deflections were monitored both as a function of (i) the scan rate (≤20 mV s−1) and (ii) the time for potential step experiments at oxidizing (>+0.4 V) and reducing (<+0.2 V) potentials. The different directions and magnitudes of the deflections for the microcantilevers, which were coated with artificial molecular muscles, were compared with (i) data from nominally bare microcantilevers precoated with gold and (ii) those coated with two types of control compounds, namely, dumbbell m...

Photoconductance and inverse photoconductance in films of functionalized metal nanoparticles

Abstract: A photoconductor is a material whose electrical conductivity changes when illuminated — invariably increasing in response to the incident light. Now Nakanishi et al. show how nanoparticle-based materials can be engineered, through careful choice of the molecules used to stabilize the nanoparticles, to exhibit negative (or 'inverse') photoconductance — thin films of these materials become less conducting in the presence of light. Nanoparticle-based photoconductors based on the principles underlying these observations could find use as chemical sensors. A photoconductor is a material in which electrical conductivity changes when it is illuminated — invariably increasing in response to impinging light. However, here it is shown that nanoparticle-based materials can be engineered, through the careful choice of the molecules used to stabilize the nanoparticles, to exhibit negative photoconductance: conductivity in these materials decreases in the presence of light. In traditional photoconductors1,2,3, the impinging light generates mobile charge carriers in the valence and/or conduction bands, causing the material’s conductivity to increase4. Such positive photoconductance is observed in both bulk and nanostructured5,6 photoconductors. Here we describe a class of nanoparticle-based materials whose conductivity can either increase or decrease on irradiation with visible light of wavelengths close to the particles’ surface plasmon resonance. The remarkable feature of these plasmonic materials is that the sign of the conductivity change and the nature of the electron transport between the nanoparticles depend on the molecules comprising the self-assembled monolayers (SAMs)7,8 stabilizing the nanoparticles. For SAMs made of electrically neutral (polar and non-polar) molecules, conductivity increases on irradiation. If, however, the SAMs contain electrically charged (either negatively or positively) groups, conductivity decreases. The optical and electrical characteristics of these previously undescribed inverse photoconductors can be engineered flexibly by adjusting the material properties of the nanoparticles and of the coating SAMs. In particular, in films comprising mixtures of different nanoparticles or nanoparticles coated with mixed SAMs, the overall photoconductance is a weighted average of the changes induced by the individual components. These and other observations can be rationalized in terms of light-induced creation of mobile charge carriers whose transport through the charged SAMs is inhibited by carrier trapping in transient polaron-like states9,10. The nanoparticle-based photoconductors we describe could have uses in chemical sensors and/or in conjunction with flexible substrates.

Active molecular plasmonics: controlling plasmon resonances with molecular switches.

Abstract: A gold nanodisk array, coated with bistable, redox-controllable [2]rotaxane molecules, when exposed to chemical oxidants and reductants, undergoes switching of its plasmonic properties reversibly. By contrast, (i) bare gold nanodisks and (ii) disks coated with a redox-active, but mechanically inert, control compound do not display surface-plasmon-based switching. Along with calculations based on time-dependent density functional theory, these experimental observations suggest that the nanoscale movements within surface-bound "molecular machines" can be used as the active components in plasmonic devices.

Mesostructured multifunctional nanoparticles for imaging and drug delivery

Abstract: Mesostructured silica particles (∼100 nm diameter with ∼2 nm pores) prepared by surfactant-templated sol–gel techniques are versatile supports that can be easily derivatized with active molecules to create multifunctional materials. By deliberately placing active molecules in different regions of the mesostructure, fluorescent molecules, molecular machines, targeting ligands, and metal nanocrystals can be combined on a single particle. This review highlights the research in which multiple components are incorporated onto mesoporous silica for simultaneous imaging and delivery of molecules in biological applications.

Acid-base actuation of [c2]daisy chains.

Abstract: A versatile synthetic strategy, which was conceived and employed to prepare doubly threaded, bistable [c2]daisy chain compounds, is described. Propargyl and 1-pentenyl groups have been grafted onto the stoppers of [c2]daisy chain molecules obtained using a template-directed synthetic protocol. Such [c2]daisy chain molecules undergo reversible extension and contraction upon treatment with acid and base, respectively. The dialkyne-functionalized [c2]daisy chain (AA) was subjected to an [AA+BB] type polymerization with an appropriate diazide (BB) to afford a linear, mechanically interlocked, main-chain polymer. The macromolecular properties of this polymer were characterized by chronocoulometry, size exclusion chromatography, and static light-scattering analysis. The acid−base switching properties of both the monomers and the polymer have been studied in solution, using 1H NMR spectroscopy, UV/vis absorption spectroscopy, and cyclic voltammetry. The experimental results demonstrate that the functionalized [c...

A Light-Gated STOP−GO Molecular Shuttle

Abstract: Degenerate [2]rotaxanes, with their two identical binding sites, generally exhibit equilibrium dynamics with free energies of activation (ΔG‡) for the shuttling process starting as low as 10 kcal·mol−1. This ΔG‡ value can be raised quite dramatically by inserting “speed bumps” in the form of steric and/or electrostatic barriers into the linkers between the two identical binding sites. In our more recent research targeted toward the exploitation of the 4,4′-azobiphenyloxy unit (ABP) as a light-operated gate, we decided to introduce (i) four methyl groups on the one hand and (ii) four fluorine atoms on the other, at the 3,5,3′,5′-positions of the ABP units to curtail binding by the CBPQT4+ ring if not sterically in the case of i, then electronically in the case of ii. The first approach led to a gate (ABP-Me4) that remains closed all the time, whereas the second approach affords a gate (ABP-F4) that we can close with UV light and open with visible light. Herein, we show how light can be used, in conjunction...

Metal nanoparticles functionalized with molecular and supramolecular switches.

Abstract: Weakly protected metal nanoparticles (MNPs) are used as precursors for the preparation of catenane- and pseudorotaxane-decorated NPs of various compositions (gold, palladium, platinum). When attached to the surface of MNPs, the molecular switches retain their switching abilities. The redox potentials of these switches depend on and can be regulated by the composition of the mixed self-assembled monolayers covering the MNPs.

Thither supramolecular chemistry

Abstract: The way forward for a field in its infancy is to focus on complexity and integrated systems that may lead to emergent phenomena, suggests J. Fraser Stoddart at Northwestern University.

Dynamic hook-and-eye nanoparticle sponges

Abstract: Systems in which nanoscale components of different types can be captured and/or released from organic scaffolds provide a fertile basis for the construction of dynamic, exchangeable functional materials. In such heterogeneous systems, the components interact with one another by means of programmable, noncovalent bonding interactions. Herein, we describe polymers that capture and release functionalized nanoparticles selectively during redox-controlled aggregation and disaggregation, respectively. The interactions between the polymer and the NPs are mediated by the reversible formation of polypseudorotaxanes, and give rise to architectures ranging from short chains composed of few nanoparticles to extended networks of nanoparticles crosslinked by the polymer. In the latter case, the polymer/nanoparticle aggregates precipitate from solution such that the polymer acts as a selective 'sponge' for the capture/release of the nanoparticles of different types.

Mesostructured Silica for Optical Functionality, Nanomachines, and Drug Delivery.

Abstract: Silica thin films and nanoparticles prepared using sol-gel chemistry are derivatized with active molecules to generate new functional materials. The mild conditions associated with sol-gel processing allow for the incorporation of a range of dopants including organic or inorganic dyes, biomolecules, surfactants, and molecular machines. Silica nanoparticles embedded with inorganic nanocrystals, and films containing living cells have also been synthesized. Silica templated with surfactants to create mesostructure contains physically and chemically different regions that can be selectively derivatized using defined techniques to create dynamic materials. Using two different techniques, donor-acceptor pairs can be doped into separated regions simultaneously and photo-induced electron transfer between the molecules can be measured. Mesoporous silica materials are also useful supports for molecular machines. Machines including snap-tops and nanoimpellers that are designed to control the release of guest molecules trapped within the pores are described. Mesoporous silica nanoparticles are promising materials for drug delivery and other biomedical applications because they are nontoxic and can be taken up by living cells. Through appropriate design and synthesis, multifunctional mesoporous silica nanoparticles for sophisticated bio-applications are created.

A push-button molecular switch.

Abstract: The preparation, characterization, and switching mechanism of a unique single-station mechanically switchable hetero[2]catenane are reported. The facile synthesis utilizing a “threading-followed-by-clipping” protocol features the Cu2+-catalyzed Eglinton coupling as a mild and efficient route to the tetrathiafulvalene-based catenane in high yield. The resulting mechanically interlocked molecule operates as a perfect molecular switch, most readily described as a “push-button,” whereby two discrete and fully occupied translational states are toggled electrochemically at incredibly fast rates. This mechanical switching is probed using a wide variety of experimental techniques as well as by quantum mechanical investigations. The fundamental distinctions between this single-station [2]catenane and other more traditional bi- and multistation molecular switches are significant.

Rigid-Strut-Containing Crown Ethers and [2]Catenanes for Incorporation into Metal–Organic Frameworks

Abstract: To introduce crown ethers into the struts of metal-organic frame- works (MOFs), general approaches have been developed for the syntheses of dicarboxylic acid dibenzo(30)crown- 10 (DB30C10DA), dicarboxylic acid di- 2,3-naphtho(30)crown-10 (DN30C10DA), dicarboxylic acid bis- paraphenylene(34)crown-10 (BPP34C10DA), and dicarboxylic acid 1,5-naphthoparaphenylene(36)crown-10 (NPP36C10DA). These novel crown ethers not only retain the characteris- tics of their parent crown ethers since they can 1) bind cationic guests and 2) serve as templates for making me- chanically interlocked molecules

Facile postpolymerization end‐modification of RAFT polymers

Abstract: One-pot methods for the end-group postpolymerization modification of reversible addition fragmentation chain transfer (RAFT) derived polymers were investigated. Dithioester-terminated polymers were transformed into ω-functionalized polymers through conjugate addition of a variety of acrylates with an intermediate thiol. These methods provide a versatile means of introducing a variety of functionalities onto the polymer terminus, while simultaneously removing the residual dithiobenzoate group. A series of functionalized polymethylmethacrylate-b-polystyrene (PMMA-b-PS) polymers were synthesized utilizing the developed methods to probe the effect of charged end groups on diblock copolymer phase separation in thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 346–356, 2009

Assembly of polygonal nanoparticle clusters directed by reversible noncovalent bonding interactions.

Abstract: The reversible molecular template-directed self-assembly of gold nanoparticles (AuNPs), a process which relies solely on noncovalent bonding interactions, has been demonstrated by high-resolution transmission electron microscopy (HR-TEM). By employing a well-known host-guest binding motif, the AuNPs have been systemized into discrete dimers, trimers, and tetramers. These nanoparticulate twins, triplets, and quadruplets, which can be disassembled and reassembled either chemically or electrochemically, can be coalesced into larger, permanent polygonal structures by thermal treatment using a focused HR-TEM electron beam.

Molecular, Supramolecular, and Macromolecular Motors and Artificial Muscles

Abstract: Recent developments in chemical synthesis, nanoscale assembly, and molecular-scale measurements enable the extension of the concept of macroscopic machines to the molecular and supramolecular levels. Molecular machines are capable of performing mechanical movements in response to external stimuli. They offer the potential to couple electrical or other forms of energy to mechanical action at the nano- and molecular scales. Working hierarchically and in concert, they can form actuators referred to as artificial muscles, in analogy to biological systems. We describe the principles behind driven motion and assembly at the molecular scale and recent advances in the field of molecular-level electromechanical machines, molecular motors, and artificial muscles. We discuss the challenges and successes in making these assemblies work cooperatively to function at larger scales.

Heterogeneous Catalysis of a Copper-Coated Atomic Force Microscopy Tip for Direct-Write Click Chemistry

Abstract: We report a constructive scanning probe lithography method that uses heterogeneous copper-coated atomic force microscopy tips to catalyze azide–alkyne cycloadditions (CuAAC) between solvated terminal alkyne molecules and azide-terminated self-assembled monolayers on silicon surfaces. Spatially controlled surface functionalization was carried out successfully with 50 mM ethanolic solutions of small molecules bearing terminal alkyne groups—propargylamine, 4-pentynoic acid, and an alkynyl-oligoethyleneoxide. We observed that reaction occurs only where the copper tip is in contact with an azide-terminated surface resulting in features with linewidths on the order of 50 nm. The extent of surface functionalization, as measured by changes in surface topography and lateral force microscopy, depends on the scanning force (31–350 nN) and scanning speed, with significant surface patterning observed even at speeds as high as 64 μm/s. In contrast with related SPL techniques, this approach affords a direct-write lithographic approach to modifying and patterning surfaces constructively at the nanoscale without the need for auxiliary reagents. All that is required is (1) an azide surface (2) a solution of a terminal alkyne and (3) a copper-coated AFM tip. These advantages allow the direct attachment of a potentially limitless library of molecules that bear terminal alkyne functionalities—including biomolecules—under relatively mild conditions, with sub-100 nm spatial resolution.

Synthesizing interlocked molecules dynamically.

Abstract: As the complexity of mechanically interlocked molecular architectures increases, it is important to understand the underlying principles, such as molecular recognition and self-assembly processes, that govern the practice of template-directed synthesis necessary to create these particular compounds. In this review, we explain the importance of dynamic processes in the synthesis of mechanically interlocked compounds. We show how many different dynamic covalent bonds have been used in the synthesis of rotaxanes, catenanes, and other higher-order mechanically interlocked compounds, with the goal of revealing the state of the art in dynamic covalent chemistry.

A bistable poly[2]catenane forms nanosuperstructures

Abstract: Side-chain poly[2]catenanes at the click of a switch! A bistable side-chain poly[2]catenane has been synthesized and found to form hierarchical self-assembled hollow superstructures of nanoscale dimensions in solution. Molecular electromechanical switching (see picture) of the material is demonstrated, and the ground-state equilibrium thermodynamics and switching kinetics are examined as the initial steps towards processible molecular-based electronic devices and nanoelectromechanical systems.

Complexation between methyl viologen (paraquat) bis(hexafluorophosphate) and dibenzo[24]crown-8 revisited.

Abstract: Paraquat bis(hexafluorophosphate) undergoes stepwise dissociation in acetone. All three species-the neutral molecule, and the mono- and dications-are represented significantly under the experimental conditions typically used in host-guest binding studies. Paraquat forms at least four host-guest complexes with dibenzo[24]crown-8. They are characterized by both 1:1 and 1:2 stoichiometries, and an overall charge of either zero (neutral molecule) or one (monocation). The monocationic 1:1 host-guest complex is the most abundant species under typical (0.5-20 mM) experimental conditions. The presence of the dicationic 1:1 host-guest complex cannot be excluded on the basis of our experimental data, but neither is it unambiguously confirmed to be present. The two confirmed forms of paraquat that do undergo complexation-the neutral molecule and the monocation-exhibit approximately identical binding affinities toward dibenzo[24]crown-8. Thus, the relative abundance of neutral, singly, and doubly charged pseudorotaxanes is identical to the relative abundance of neutral, singly, and doubly charged paraquat unbound with respect to the crown ether in acetone. In the specific case of paraquat/dibenzo[24]crown-8, ion-pairing does not contribute to host-guest complex formation, as has been suggested previously in the literature.