Dibenzo-18-crown-6 Research Articles

Proton Conduction in Tröger's Base-Linked Poly(crown ether)s.

Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host-guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers-poly(TBL-DB18C6)- t and poly(TBL-DB18C6)- c-synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)- t, which is found to be 1.4 × 10-4 mS cm-1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

Structure, Dynamics, and Adsorption of Charged Guest within the Nanocavity of Polymer-Functionalized Neutral Macrocyclic Host.

Host-guest encapsulation has been widely applied for purification and seizing of the metal ions. Macrocyclic crown ethers are one of the most popular hosts in the field of host-guest chemistry, which on functionalization with polymers are employed as an effective adsorbent. In spite of their vast applications, the microscopic information about their sensing mechanism toward cations/molecules is very scarce. Therefore, the present study is focused on the molecular insights of ion-exchange mechanism within the cavity of crown ether-functionalized polymers using molecular dynamics (MD) simulations. This present study investigates the molecular-level events of chloromethylated polystyrene (CMPS) bearing dibenzo-18-crown-6 (DB18C6) in the aqueous and acidic environment, which has been found to be particularly successful in sensing of various alkali and alkali earth metal ions. A strategy has been envisaged to design a crown ether-based functionalized polymeric resin, which exhibits good match of properties with the in-house-synthesized resin. The MD studies well capture the experimentally observed Langmuir-type adsorption isotherms of Li+ ions on crown ether-grafted polymer resins. The presence of acid reduces the adsorption of Li+ ions due to the competition with H3O+ ions. In addition, the results revealed that the "adsorption in crown cavity" follows a dual residence time function. To the best of our knowledge, this is the first report on the adsorption isotherm of functionalized crown ether using MD simulations. The structure and dynamics of binding sites were explored using radial distribution functions and diffusion coefficients. All of these effects have been studied for different Li+-ion concentrations, acid concentrations, and counterions as well as different lengths of polymer chains and degrees of polymerization. Overall, the present study provides insights into and quantitative information about adsorption on the CMPS-DB18C6 resin, which might be useful in myriads of host-guest-based adsorption experiments.

Selective transport of zirconium (IV) and niobium (V) from hydrochloric media through a bulk liquid membrane

The selective transport of zirconium/niobium from hydrochloric medium has been investigated through a bulk liquid membrane (BLM) using tri-n-butyl-phosphate (TBP), tri-n-octylamine and dibenzo-18-crown-6 (DBC-6) as the extractants (carriers). The Optimization studies have been carried out by scrutinizing the effect of variables such as the hydrochloric acid concentration in the feed solution, membrane type and hydrochloric acid concentration in the strip solution using the Taguchi approach. The Quantitative transport of zirconium/niobium has been observed by 30% (v/v) TBP in 1200 min from the feed composed of a 9.0 M hydrochloric acid solution of Zr(IV), Nb(V) and lanthanide cations, while the transport of other cations, which have been presented along with Zr/Nb are less than 3% during the same time. Moreover, the possible mechanism of Zr(IV)/Nb(V) ion transport through the BLM has also been discussed and the results show a consecutive, irreversible second-order reaction at the interfaces. Transfer kinetics studies show that niobium transfer process exhibits slightly faster kinetics than zirconium.

Constructing supramolecular polymers from phototrigger containing monomer

A new type of photo-induced supramolecular polymer was fabricated by host-guest interaction from a phototrigger containing building block. A dibenzo-24-crown-8 (DB24C8) macrocycle and dibenzylammonium (DBA) site containing linear monomer was designed and synthesized. The coumarin, as a photocleavable protector, was introduced to the terminal of the monomer. When exposed to the UV light, the coumarin unit would be cleavaged and the monomer without terminal coumarin can self-assemble into supramolecular polymers via the host-guest interaction between DB24C8 moieties and DBA units. Increasing the concentration of the monomer, the supramolecular polymers will convert to supramolecular organogel by cross-linking with each other.

Microhydration of Dibenzo-18-Crown-6 Complexes with K+, Rb+, and Cs+ Investigated by Cold UV and IR Spectroscopy in the Gas Phase.

In this Article, we examine the hydration structure of dibenzo-18-crown-6 (DB18C6) complexes with K+, Rb+, and Cs+ ion in the gas phase. We measure well-resolved UV photodissociation (UVPD) spectra of K+·DB18C6·(H2O) n, Rb+·DB18C6·(H2O) n, and Cs+·DB18C6·(H2O) n ( n = 1-8) complexes in a cold, 22-pole ion trap. We also measure IR-UV double-resonance spectra of the Rb+·DB18C6·(H2O)1-5 and the Cs+·DB18C6·(H2O)3 complexes. The structure of the hydrated complexes is determined or tentatively proposed on the basis of the UV and IR spectra with the aid of quantum chemical calculations. Bare complexes (K+·DB18C6, Rb+·DB18C6, and Cs+·DB18C6) have a similar boat-type conformation, but the distance between the metal ions and the DB18C6 cavity increases with increasing ion size from K+ to Cs+. Although the structural difference of the bare complexes is small, it highly affects the manner in which each is hydrated. For the hydrated K+·DB18C6 complexes, water molecules bind on both sides (top and bottom) of the boat-type K+·DB18C6 conformer, while hydration occurs only on top of the Rb+·DB18C6 and Cs+·DB18C6 complexes. On the basis of our analysis of the hydration manner of the gas-phase complexes, we propose that, for Rb+·DB18C6 and Cs+·DB18C6 complexes in aqueous solution, water molecules will preferentially bind on top of the boat conformers because of the displaced position of the metal ions relative to DB18C6. In contrast, the K+·DB18C6 complex can accept H2O molecules on both sides of the boat conformation. We also propose that the characteristic solvation manner of the K+·DB18C6 complex will contribute entropically to its high stability and thus to preferential capture of K+ ion by DB18C6 in solution.

Integrative Self-Sorting: One-Pot Synthesis of a Hetero[4]rotaxane from a Daisy-Chain-Containing Hetero[4]pseudorotaxane.

The structural complexity of mechanically interlocked molecules are very attractive to chemists owing to the challenges they present. In this article, novel mechanically interlocked molecules with a daisy-chain-containing hetero[4]rotaxane motif were efficiently synthesized. In addition, a novel integrative self-sorting strategy is demonstrated, involving an ABB-type (A for host, dibenzo-24-crown-8 (DB24C8), and B for guest, ammonium salt sites) monomer and a macrocycle host, benzo-21-crown-7 (B21C7), in which the assembled species in hydrogen-bonding-supported solvent only includes a novel daisy-chain-containing hetero[4]pseudorotaxane. The found self-sorting process involves the integrative recognition between B21C7 macrocycles and carefully designed components simultaneously containing two types of secondary ammonium ions and a host molecule, DB24C8 crown ether. The self-sorting strategy is integrative to undertake self-recognition behavior to form one single species of pseudorotaxane compared with the previous report. This self-sorting system can be used for the efficient one-pot synthesis of a daisy-chain-containing hetero[4]rotaxane in a good yield. The structure of hetero[4]rotaxane was confirmed by 1 H NMR spectroscopy and high-resolution electrospray ionization (HR-ESI) mass spectrometry.

Interfacial Behavior of Cs+, K+, Na+, and Rb+ Extraction in the Presence of Dibenzo-18-Crown-6 from the Nitrobenzene-Water Biphasic System: Experimental, Quantum Chemical, and Molecular Dynamic Studies.

Extraction of metal ions (i.e., Cs+, K+, Na+, and Rb+) in the presence of ionophore such as dibenzo-18-crown-6 (DB18C6) from the nitrobenzene–water biphasic system is reported by COSMO-RS (conductor-like screening model for real solvents) predictions, molecular dynamics simulation, along with experimental validation. The predicted values of selectivity as obtained for the Na+–DB18C6 complex were 4.571, 4.877, and 4.947 at 298.15, 308.15, and 318.15 K, respectively. This was then confirmed by the experimental distribution coefficient (D) as obtained in the diluent systems along with by varying the metal ion to crown ether ligand (M–L) mole ratios: 10:1 (0.1 M M+ and 0.01 M DB18C6), 1:1 (0.01 M M+ and 0.01 M DB18C6), and 1:10 (0.001 M M+ and 0.01 M DB18C6). The experimentally determined values of DNa (i.e., 0.059, 0.060, and 0.056) were found to be very large as compared to the values of DCs (i.e., 0.001, 0.010, and 0.024) in the nitrobenzene phase. It indicates an excellent extraction ability of DB18C6 for Na+. The rate of phase separation for the Cs+NO3– system was slow as compared to other metal ion systems. The binding energies, free energies, and nonbonded interaction energies of the complexed metal ion in solution were calculated with both explicit and implicit solvent models. A higher interaction energy between Na+–DB18C6 complex and nitrobenzene was observed (i.e., −289.92 in the explicit model and −143.12 kcal/mol in the implicit model) when compared with other metal ions (i.e., Cs+, K+, and Rb+).

Partitioning of Cs+ and Na+ ions by dibenzo-18-crown-6 ionophore in biphasic aqueous systems of octanol and ionic liquid

Abstract Molecular dynamics (MD) simulations were carried out to obtain molecular level insights on the behavior of Cs+/Na+ ions at the water–ionic liquid and water–octanol interface in the presence of dibenzo-18-crown-6 (DB18C6) ionophore with an aim to compare an ionic liquid (IL) to a octanol as receiving organic solvent phase. It was observed that the rate of phase separation for the octanol system was rapid as compared to the IL system. The free crown ethers (CE) were found to be highly solvated by the IL phase. A dual cationic exchange mechanism was observed at the [BMIM]/water interface. The [BMIM]+ cation was found to exchange with both the metal ions in aqueous phase as well as with the metal ion aided by the ionophore. The self-diffusion coefficient of the 1:2 complex (0.07×10−9 m2/s) at the octanol/water interface were found to be smaller than that of 1:1 complex (0.37 and 0.14×10−9 m2/s). It was observed that the surface tension of ILs decreased in the presence of complexes and free CE, whereas the surface tension of water was found to increase in presence of salts (Cs+NO3 − and Na+NO3 −). The experimentally determined value of D Cs was found to be quite high in IL phase (1.595) compared to the octanol phase (0.139) in presence of CE. The kinetics of Cs+ was found to be very fast having rate with values of k 1 ^ $\widehat {{k_1}}$ =1.79×10−12 s−1 and k 2 ^ $\widehat {{k_2}}$ =0.205×10−12 s−1 in IL and water phase, respectively. The present results may help us in understanding the role of diluents in the assisted metal ion extraction but also in the future design of diluents and ionophore.

Influence of Macrocyclic Ring Size on the Corrosion Inhibition Efficiency of Dibenzo Crown Ether: A Density Functional Study

The effect of macrocycle ring size on the corrosion inhibition efficiency of dibenzo-12-crown-4 (DB12C4), dibenzo-15-crown-5 (DB15C5), dibenzo-18-crown-6 (DB18C6), dibenzo-21-crown-7 (DB21C7) and dibenzo-24-crown-8 (DB24C8) have been elucidated by mean of density functional calculation at B3LYP/6-31G(d) level of theory in the gas and aqueous environment. The quantum chemical parameters including the frontier orbital energies (EHOMO, ELUMO), ionization potential (I), electron affinity (A), the absolute electronegativity (χ), hardness (η), softness (σ), and the fraction of electron transferred (ΔN) are positively correlated to the corrosion inhibition efficiency (IE%) of the studied crown ethers. The calculation results indicate that DB24C8 exhibits the highest corrosion inhibition efficiency, whereas DB12C4 exhibits the lowest corrosion inhibition efficiency. The results of this study will contribute to design crown ethers potential as corrosion inhibitors.

Four-State Molecular Shuttling of [2]Rotaxanes in Response to Acid/Base and Alkali-Metal Cation Stimuli.

In this study, we synthesized [2]rotaxanes possessing three recognition sites-a dialkylammonium, an alkylarylamine, and a tetra(ethylene glycol) stations-in their dumbbell-like axle component and dibenzo[24]crown-8 (DB24C8) as their macrocyclic component. These [2]rotaxanes behaved as four-state molecular shuttles: i) under acidic conditions, the DB24C8 unit encircled both the dialkylammonium and alkylarylammonium stations; ii) under neutral conditions, the dialkylammonium unit was the predominant station for the DB24C8 component; iii) under basic conditions, when both ammonium centers were deprotonated, the alkylarylamine unit became a suitable station for the DB24C8 component; and iv) under basic conditions in the presence of an alkali-metal cation, the tetra(ethylene glycol) unit recognized the DB24C8 component through cooperative binding of the alkali-metal ion. In addition, we observed that the [2]rotaxanes exhibited selective recognition for metal cations. These shuttling motions of the macrocyclic component proceeded reversibly.

Polymeric Pseudo-Liquid Membranes from Polymethacrylate Derivative Bearing Oligodimethylsiloxane Unit

Novel liquid membrane system, which is named polymeric pseudo-liquid membrane was constructed from polymethacrylate derivative bearing oligodimethylsiloxane (PDMSMA), showing rubbery state under operating conditions, as a membrane matrix. In the present study, dibenzo-18-crown-6 (DB18C6), dibenzo-21-crown-7 (DB21C7) or O -allyl- N -(9-anthracenylmethyl)cinchonidinium bromide (AMCC) was adopted as a carrier for KCl transport, CsCl transport or optical resolution of racemic mixture of phenylglycine (Phegly), respectively. The results of KCl and CsCl transports revealed that the membrane transport was attained by carrier-diffusion mechanism like conventional liquid membranes. The present study led the conclusion that PDMSMA can be applicable not only to membrane transport of alkali metal ions, such as K + and Cs + , but also to chiral separation.

Automatic potentiometric system for quantification of three imidazole derivatives based on new polymeric PVC membrane sensors

New potentiometric monitoring devices for trace and fast determination of three imidazole derivatives were presented. The sensing materials were fabricated by the inclusion of imidazolinium phosphomolybdate (Imd/PMA) (sensor I), imidazolinium tetraphenylborate (Imd/TPB) (sensor II), or dibenzo-24-crown-8 (DB24C8) (sensor III) in the plasticized polyvinyl chloride (PVC) matrix. The sensors showed clear enhanced response towards imidazolium [Imd+] ions over the concentration range 4.0 × 10−6–1 × 10−2 mol L−1 at pH 5 with 0.42 μg mL−1 as a detection limit. The selectivity was tested with various inorganic and nitrogenous organic ions. Long life span, fast response, long-term stability, and high reproducibility are shown for the sensors. Method validation for the proposed method was achieved by quantifying the detection limit, linear range, accuracy, precision, repeatability, and between-day variability. It revealed good performance characteristics of the proposed sensors. The applicability of the sensors for analyzing imidazole in urine samples was successfully demonstrated via recovery studies.

Geometric and Electronic Structures of Dibenzo-15-Crown-5 Complexes with Alkali Metal Ions Studied by UV Photodissociation and UV-UV Hole-Burning Spectroscopy.

We measure UV photodissociation (UVPD) and UV-UV hole-burning (HB) spectra of dibenzo-15-crown-5 (DB15C5) complexes with alkali metal ions, M+·DB15C5 (M = Li, Na, K, Rb, and Cs), under cold (∼10 K) conditions in the gas phase. The UV-UV HB spectra of the M+·DB15C5 (M = K, Rb, and Cs) complexes indicate that there is one dominant conformation for each complex except the Na+·DB15C5 complex, which has two conformers with a comparable abundance ratio. It was previously reported that the M+·(benzo-15-crown-5) (M+·B15C5, M = K, Rb, and Cs) complexes each have three conformers. Thus, the attachment of one additional benzene ring to the crown cavity of benzo-15-crown-5 reduces conformational flexibility, giving one dominant conformation for the M+·DB15C5 (M = K, Rb, and Cs) complexes. In the UVPD spectra of the K+·DB15C5, Rb+·DB15C5, and Cs+·DB15C5 complexes, the S1-S0 and S2-S0 transitions are observed independently at different positions with different vibronic structures. The spectral features are substantially different from those of the K+·(dibenzo-18-crown-6) (K+·DB18C6) complex, which belongs to the C2v point group and exhibits exciton splitting with an interval of 2.7 cm-1. The experimental and theoretical results suggest that in the M+·DB15C5 complexes the two benzene rings are not symmetrically equivalent with each other and the S1-S0 and S2-S0 electronic excitations are almost localized in one of the benzene rings. The electronic interaction energy between the two benzene chromophores is compared between the K+·DB15C5 and K+·DB18C6 complexes by quantum chemical calculations. The interaction energy of the K+·DB15C5 complex is estimated to be less than half of that of the K+·DB18C6 complex (∼30 cm-1) due to less suitable relative angles between the transition dipole moments of the two benzene chromophores in K+·DB15C5.

Cationic and Neutral Rotaxanes Having Different Functional Groups in the Axle Molecule and Their Coordination to PtII.

Dibenzo[24]crown-8 (DB24C8) forms rotaxanes with a linear molecule having a dialkylammonium group and a triazole group as well as with the acetylation product of a cationic axle molecule. The former cationic rotaxane is stabilized by multiple intermolecular hydrogen bonds between the NH2+ and oxyethylene groups. The neutral rotaxane contains the macrocycle in the vicinity of the terminal aryl group. The co-conformation of both the cationic and neutral rotaxanes can be fixed by coordination of the triazole group of the axle molecule to PtCl2 (dmso)2 . A 1 H NMR spectroscopic study on the thermodynamics of the Pt coordination revealed a larger association constant for the rotaxanes than for the corresponding axle molecules and a larger value for the neutral rotaxane than for the cationic rotaxane.

One-pot synthesis of hetero[6]rotaxane bearing three different kinds of macrocycle through a self-sorting process.

In this article, a six-component self-sorting process that involves three types of crown ether macrocycle and three types of cation guest molecule was carefully and thoroughly investigated. The six components include three kinds of crown ether, namely bis(p-phenylene-34-crown-10) (BPP34C10), dibenzo-24-crown-8 (DB24C8) and benzo-21-crown-7 (B21C7), and their corresponding cation guest molecules, namely a 4,4'-bipyridine dication (BPY2+) and dibenzylammonium (DBA) and benzylalkylammonium (BAA) ions, respectively. Based on this well-established highly selective six-component self-sorting process, a hetero[6]rotaxane bearing three different kinds of crown ether macrocycle was designed and successfully synthesized through a facile and efficient one-pot "click" stoppering strategy. Such work is proposed to be a significant advance in the construction of mechanically interlocked molecules with high structural complexity, as well as a good supplement in the areas of multi-component self-sorting and noncovalent self-assembly.

Preconcentration and speciation of thallium by ferrofluid based dispersive solid phase extraction and flame atomic absorption spectrometry

A dispersive solid phase extraction method based on ferrofluid has been proposed for the separation and preconcentration of thallium (I) before its determination by flame atomic absorption spectrometry. The ferrofluid was rapidly injected into the aqueous sample containing the thallium (I) and dibenzo-18-crown-6 (DB18C6) as the chelating agent with a syringe. The separation of the sorbent from the aqueous phase was achieved by the application of an external magnet. The main factors affecting the extraction of thallium (I) were investigated and optimized. Total thallium was determined after the reduction of Tl(III) to Tl(I) by hydroxylamine hydrochloride. Under the optimized conditions with a sample volume of 150.0mL, the detection limit (based on 3Sb/m) and the enhancement factor were found to be 0.85μgL–1 and 298, respectively. The relative standard deviation at 50μgL–1 concentration level of Tl(I) was 3.2%. The method was successfully applied to the determination of thallium species in water and waste water samples as well as total thallium in nail, hair, cabbage and iron ore samples. The validity of the method was checked through the recovery experiments besides the analysis of a certified reference material.

Recognition and Quantification of Some Monoamines Neurotransmitters

AbstractThree neurotransmitter sensors for dopamine, serotonin, and epinephrine have been developed. Potentiometric sensors for serotonin and epinephrine are novel and first to be introduced. The neurotransmitter potentiometric sensors are based on using dibenzo‐30‐crown‐10 (DB30C10), dibenzo‐24‐crown‐8 (DB24C8), and dibenzo‐18‐crown‐6 (DB18C6) as ionophores and neutral carriers incorporating in poly(vinyl chloride) matrix membrane plasticized with o‐nitrophenyl octyl ether. Sensors based on dibenzo‐30‐crown‐10 show good responses for the dopamine, serotonin, and epinephrine (Type I–III, respectively) with a cationic slope of 57.9 mV decade−1 and detection limit of 4.0×10−5 mol L−1 dopamine, cationic slope of 55.9 mV decade−1 and detection limit of 4.0×10−5 mol L−1 serotonin, and cationic slope of 54.4 mV decade−1 and detection limit of 2.0×10−5 mol L−1 epinephrine. The sensors based on DB24C8 and DB18C6 (Types IV–IX) show poor responses in terms of calibration range and slope. The effect of the interferents on the response of the sensors reveals a high selectivity for the neurotransmitters over many inorganic cations, ascorbic and uric acids. The useful pH range for the three sensors is 3–7, the response time is fast (11 s), and the life span is long (2.5 months). Sensors (Types I and III) are successfully used for the quantification of dopamine and adrenaline in pharmaceutical preparations.

Interfacial insights on the dibenzo-based crown ether assisted cesium extraction in [BMIM][Tf2N]–water binary system

The distribution coefficient of Cs is estimated using dibenzo-21-crown-7 (DB21C7) and di-benzo-18-crown-6 (DB18C6) in 1-butyl-3-methylimidazolium bis (trifluroromethanesulphonyl) imide (BMIMTF2N) ionic liquid by performing solvent extraction experiments. In addition, molecular dynamics studies on the extraction of cesium (Cs+) ion transfer from the aqueous phase to the BMIMTF2N phase is reported. The experimental findings gave a cesium distribution coefficient of 0.218 and 0.326, which agrees closely with the values of 0.2 and 0.5 obtained from MD simulation for the ionophores DB18C6 and DB21C7, respectively. Thus MD simulation may be helpful in screening the solvents prior to the experiments.

The role of macrocyclic compounds in the extraction and possible separation of platinum and rhodium from chloride solutions.

Macrocyclic compounds (crown ethers), specifically 18-crown-6 (18-C-6), benzo-15-crown-5 (B-15-C-5), di-benzo-18-crown-6 (DB-18-C-6) and di-cyclohexano-18-crown-6 (DC-18C-6), are used as extractants as well as synergists with amine-group extractants. Platinum and rhodium belong to platinum-group metals (PGMs) and have very similar ionic radii and similar properties. The separation of PGMs is most useful for the preparation of functional materials. Macrocyclic compounds are tested for platinum and rhodium separation and are found to achieve marginal separation. Amines (used as extractants) are paired with macrocyclic compounds (used as synergists), and the separation factor between platinum and rhodium is increased with synergistic enhancement from a chloride solution. The present study discusses extraction chemistry, separation factors and the synergy between platinum and rhodium from chloride solutions. To ensure accurate data, the aqueous samples in this study are analyzed using an inductively coupled plasma optical emission spectrometer (ICP-OES).

Reverse Anomeric Effect in Large-Amplitude Pyridinium Amide-Containing Mannosyl [2]Rotaxane Molecular Shuttles.

The reverse anomeric effect (RAE) was investigated in different mannosyl [2]rotaxane molecular shuttle isomers that contain dibenzo-24-crown-8 (DB24C8) as the macrocycle, and anilinium and pyridinium amide as molecular stations. The switching on or off of the RAE was possible depending on both the pyridinium amide motif and the localization of the DB24C8 along the thread. The (1) C4 mannopyranosyl chair-like conformation was observed in all the non-interlocked molecules because the anomeric carbon of the mannose is linked to the positively charged nitrogen of the pyridinium unit. In the protonated rotaxanes, the (1) C4 chair conformation of the mannose end remains because the DB24C8 resides around the best anilinium station, which is located at the other end of the axle. Upon deprotonation of the anilinium, the DB24C8 shuttles with a large-amplitude motion toward the pyridinium amide stations, where it interacts in a different fashion depending on the pyridinium motif. In one molecular shuttle, the RAE could be switched on or off with control at one end of the encircled thread upon protonation/deprotonation of the other end, through shuttling of the DB24C8.