Spectroscopic and thermodynamic studies of binary mixtures composed of nematogenic and non-nematogenic components

The effect of a non-nematic guest, tetracyanoethylene (TCNE), on the liquid-crystaline state of the host, 4-n-pentyl-4'-cyanobiphenyl (5CB), has been investigated. It was shown by absorption spectroscopy that TCNE forms a 1 : 1 charge transfer complex with 5CB in the nematic phase, similar to that in the isotropic solution. The effect of TCNE on the transition temperature was investigated by comparison with a normal guest, 2,3-dimethylbutane (DMB), which has a molecular volume comparable with that of TCNE but has no specific interaction with the host. TCNE was found to lower the transition temperature much more strikingly than DMB, suggesting the peculiar effect of complex formation. The theoretical background is given based on molecular field theory.     

Mesophase study of pure and doped cyanobiphenyl liquid crystals with salen-type systems

Two salen Schiff base ligands derived from the condensation of ethylendiamine on salicylaldehyde and 5-chlorosalicylaldehyde, namely N,N′-bis(salicylidene)ethylene-diamine (L1) and N,N′-bis(5-chlorosalicylidene)ethylene-diamine (L2) as well as two of their iron(III) and nickel(II) complexes, were prepared and then used as doping agents of two thermotropic liquid crystals (LCs) of cyanobiphenyl type, namely 4-cyano-4′-n-pentyl-biphenyl (5CB) and 4-cyano-4′-n-octyl-biphenyl (8CB). The study of the mesophase of pure and doped LCs was carried out by UV–visible spectroscopy equipped with a heating compartment for precise temperature control, differential scanning calorimetry and polarised optical microscopy. The characteristic nematic/isotropic and smectic-A/nematic transition temperatures of 5CB- and 8CB-based systems were measured and then compared to those of the literature concerning pure 5CB and 8CB. Optical microscopy results revealed the existence of Schlieren and focal conic textures of the nematic and smectic states, respectively, both of pure and doped LCs. The homogeneity of the obtained guest–host systems was proven by the linear evolution of their transition temperatures as function of the solute concentration, with correlation factors close to unity.     

A host-induced intramolecular charge-transfer complex and light-driven radical cation formation of a molecular triad with cucurbit[8]uril

The host-guest chemistry of systems containing a molecular triad Ru(bpy) 3-MV (2+)-naphthol complex (denoted as Ru (2+)-MV (2+)-Np, 1) and cucurbit[8]uril (CB[8]) is investigated by NMR, ESI-MS, UV-vis, and electrochemistry. The Ru (2+)-MV (2+)-Np guest and CB[8] host can form a stable 1:1 inclusion complex, in which the naphthalene residue is back-folded and inserted together with the viologen residue into the cavity of CB[8]. The selective binding of Ru (2+)-MV (2+)-Np guest with beta-CD and CB[8] host is also investigated. We find that CB[8] binds the Ru (2+)-MV (2+)-Np guest stronger than beta-CD. Upon light irradiation, a MV (+*) radical cation stabilized in the cavity of CB[8] accompanied by the naphthalene residue has been observed. This novel system may open a new way for design and synthesis of photoactive molecular devices.     

Molecular dynamics simulation study of the structural features and inclusion capacities of cucurbit[6]uril derivatives in aqueous solutions

Molecular dynamics (MD) simulations were performed for cucurbit[6]uril (CB6) methyl and cyclohexyl derivatives in aqueous solutions. Furthermore, MD simulations have been conducted to study the inclusion complexes between each CB6 derivative with α,ω-pentane diammonium ion (NH₃⁺(CH₂)₅NH₃⁺) to estimate the binding free energies, the complex geometries and the intermolecular forces responsible for complex formation. Results show a complete inclusion of the guest molecule in the cavity of the host for all complexes. Results also indicate that the guest dynamics inside the cavity of the substituted host is similar to that for the unsubstituted host. This demonstrates that the molecular recognition of the host is not affected by the alkyl substitution at the equator. Also, there is an insignificant conformational change of the macrocyclic structure upon inclusion of the guest. Molecular mechanics/Poisson Boltzmann surface area method was used to estimate the binding free energy of each complex. Results indicate that host–guest electrostatic interactions make the largest contribution to the complex binding free energy. Moreover, van der Waals interactions add significantly to the complex stability. The guest molecules show more or less similar binding free energies with the substituted CB6 that exhibits slightly more negative values than unsubstituted CB6 which is proved also by umbrella sampling.     

Dielectric analysis of the interaction of nematic liquid crystals with carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) have been shown to self-organise, and when added as a guest to form a nanocomposite, their director couples with an organic liquid crystal (LC) host. Here, effects of MWCNTs on the low-frequency dielectric properties and Fréedericksz transition of the LC 4-cyano-4?-pentylbiphenyl (5CB) are studied. Anti-parallel electro-optic cells were filled with nanocomposites at weight percent concentrations of MWCNT to 5CB of: 0 (neat), 0.01, 0.10, 0.20, and 0.50. Low concentration was chosen to minimise Van der Waals attraction normally responsible for aggregation of MWCNTs. Dielectric relaxation spectroscopy was used to study interactions between MWCNTs and 5CB at frequencies from 20 Hz to 1 MHz. We propose a mechanism based upon measurements of the complex dielectric function which suggests that MWCNTs act as a slow-moving boundary within the sample cell at low frequencies and low applied electric fields, where the MWCNTs reorient along with the 5CB LC molecules. At higher frequencies and larger applied electric fields, the 5CB molecules rotate about their long axes while motion of the MWCNTs is frozen out.     

Charge transfer interaction between the nematogen 5CB and non-liquid crystal

In general, when a non-nematic solute is added to a nematic, the nematic-isotropic phase transition temperature (T _NI) decreases with increase in non-nematic concentration. But when there are hydrogen bonded complexes or π-complexes of suitable strength formed between the nematic and the solute molecules, the T _NI can rise. Mixing of p-terphenyl or anthracene with 5CB (4-cyano-4'-pentylbiphenyl) results in a T _NI rise. On the other hand, in a binary system consisting of a substance with strong acceptor properties (e.g. tetracyanoethylene; TCNE) and nematic 5CB, T _NI fell remarkably. We have now studied the effect of intermolecular interactions on the T _NI of 5CB by using various acceptor molecules and donor molecules as solutes. We have found that for binary systems in which 5CB and a solute molecule form distinct one-to-one complexes, T _NI falls rather rapidly. When the solute molecules have a strong acceptor power, the rate of T _NI fall with solute concentration is found to be correlated well with the electonegativity of the solute molecules.     

Highly selective recognition of diols by a self-regulating fine-tunable methylazacalix[4]pyridine cavity: guest-dependent formation of molecular-sandwich and molecular-capsule complexes in solution and the solid state

The molecular recognition of methylazacalix[4]pyridine (MACP-4; 1) towards various diols was investigated by using (1)H NMR spectroscopic and X-ray diffraction analysis. As a unique macrocyclic host molecule that undergoes conformational inversions very rapidly in solution, MACP-4 has been shown to self-regulate its conformation, through the formation of different conjugations of the four bridging nitrogen atoms with their adjacent pyridine rings, to form a cavity that best fits the guest species through intermolecular hydrogen-bond, C-H...pi, and pi-pi interactions between the host and guest. As a consequence, depending upon the diol structure and geometry, MACP-4 forms a 1:1 molecular sandwich, 2:1 molecular capsule, and 1:2 butterfly-layered complex with the guests. As a result of favorable enthalpy and entropy effects, MACP-4 exhibits excellent selectivity in the recognition of resorcinol, thus resulting in a very stable 1:1 sandwich complex with resorcinol with a binding constant of 6000 (M-1). The dynamic (1)H NMR spectroscopic study demonstrated that the 1,3-alternate conformation of the macrocyclic ring of the MACP-4resorcinol complex (13) is stable at low temperature (T<243 K), and its conformational inversion requires a larger activation energy (DeltaG++=(45.5+/-2.2) kJ mol(-1)). In the presence of an excess amount of resorcinol, however, the conformational inversion of the MACP-4resorcinol complex proceeds more readily with a decreased activation energy (DeltaG++=(33.5+/-1.5) kJ mol(-1)) owing most probably to the favorable enthalpy effect of the [3...1...3]++transition state.     

Host–guest control on the formation of pinacyanol chloride H-aggregates in anionic polyelectrolyte solutions

The interactions of pinacyanol chloride (PIN), a cationic cyanine dye, with the anionic polyelectrolyte poly(acrylic acid, sodium salt) (PAA) towards enhancing H-aggregation were investigated by electronic absorption spectroscopy. We employed the cucurbit[7]uril (CB7) host to control the formation of these aggregates via host–guest binding interactions with the dye molecules. Absorption spectroscopic studies clearly demonstrate that PAA enhances the formation of PIN H-aggregates. Electrostatic interactions between the cyanine dye molecules and the polyelectrolyte chains assist the formation of H-aggregates at very low dye concentrations (ca. 10 μM). Furthermore, the presence of CB7 was found to effectively disrupt the interactions responsible for dye aggregation. Thus, CB7 completely disrupts the H-aggregates (as well as lower concentrations of J-aggregates) by forming inclusion complexes with PIN. A competing guest, 1-aminoadamantane (AD), was utilised to adjust the extent of aggregation of the cyanine dye. AD regulates aggregate formation by forming an extremely stable complex with CB7 and exerting a tight control on the CB7 concentration available to interact and bind with the dye. Our spectroscopic data clearly indicate that by varying the relative molar ratios of CB7 host, AD and polyelectrolyte acid groups, we can quantitatively control the extent of formation of PIN H-aggregates in these solutions.     

From Packed “Sandwich” to “Russian Doll”: Assembly by Charge‐Transfer Interactions in Cucurbit[10]uril

As the host possessing the largest cavity in the cucurbit[n]uril (CB[n]) family, CB[10] has previously displayed unusual recognition and assembly properties with guests but much remains to be explored. Herein, we present the recognition properties of CB[10] toward a series of bipyridinium guests including the tetracationic cyclophane known as blue box along with electron‐rich guests and detail the influence of encapsulation on the charge‐transfer interactions between guests. For the mono‐bipyridinium guest (methylviologen, MV ²⁺), CB[10] not only forms 1:1 and 1:2 inclusion complexes, but also enhances the charge‐transfer interactions between methylviologen and dihydroxynaphthalene ( HN ) by mainly forming the 1:2:1 packed “sandwich” complex (CB[10] ? 2 MV ²⁺ ?HN ). For guest 1 with two bipyridinium units, an interesting conformational switching from linear to “U” shape is observed by adding catechol to the solution of CB[10] and the guest. For the tetracationic cyclophane‐blue box, CB[10] forms a stable 1:1 inclusion complex; the two bipyridinium units tilt inside the cavity of CB[10] according to the X‐ray crystal structure. Finally, a supramolecular “Russian doll” was built up by threading a guest through the cavities of both blue box and CB[10].     

Influence of electrostatic interactions on the properties of cyanobiphenyl liquid crystals predicted from atomistic molecular dynamics simulations

The influence of force field details in all-atom molecular dynamics (MD) simulations on the predicted thermodynamic, structural, and dynamic properties of bulk 4-cyano-4?-pentylbiphenyl (5CB) systems have been investigated in the 292–368 K temperature range. The effect of the molecular dipole moment and the details of dihedral potential for biphenyl unit were investigated using both polarisable (POL) and non-polarisable (NP) versions of the quantum chemistry-based force field. The predicted densities for the nematic and isotropic phases of bulk 5CB were found to be in excellent agreement with available experimental data. The nematic-isotropic transition temperature (T_NI) showed strong sensitivity to the force field details, MD simulations with partial atomic charge distributions and molecular dipole moment corresponding to high-level quantum chemistry calculations predicted an overestimation of the T_NI by about 30 K. Rescaling the charges to allow the molecular dipole to be closer to experimentally reported values of 5CB dipole in condensed phases, significantly improved the prediction of T_NI as well as other thermodynamic and dynamic properties of 5CB. We also discuss how the structural, thermodynamic, and dynamic properties of bulk 5CB are affected by the flexibility of the central biphenyl dihedral and the inclusion of induced polarisation effects.     

Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT⁴⁺ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.     

Encapsulation of a β-carboline in cucurbit[7]uril

Inclusion of a biological photosensitizer and prototype of β-carbolines, norharmane (NHM), into the cavity of cucurbit[7]uril (CB[7]) has been investigated for the first time, by using ¹H NMR and UV–visible spectroscopy, and ab initio calculations. Protonated NHM forms a very stable host–guest complex with CB[7] in aqueous solution, with a binding constant of (9.0 ± 0.5) × 10⁴ M^?1. The encapsulation of NHM into CB[7] has driven the prototropic equilibrium of NHM to protonated NHM (NHMH⁺) at neutral pH. A pH titration for the host–guest complex revealed a moderate shift of the acid–base equilibrium in the ground-state (from 7.2 to 7.9), which may be caused by the low polarity microenvironment of the CB[7] cavity. The CB[7] provides a binding pocket for the hydrophobic molecule, and the polar, carbonyl-lined portals offering an anchoring site for the positive charge of the cationic species NHMH⁺.     

Host–Guest Complexation Using Pillar[5]arene Crystals: Crystal-Structure Dependent Uptake,Release, and Molecular Dynamics of an Alkane Guest

Host–guest complexation has been mainly investigated in solution, and it is unclear how guest molecules access the assembled structures of host and dynamics of guest molecules in the crystal state. In this study, we studied the uptake, release, and molecular dynamics of n-hexane vapor in the crystal state of pillar[5]arenes bearing different substituents. Pillar[5]arene bearing 10 ethyl groups yielded a crystal structure of herringbone-type 1:1 complexes with n-hexane, whereas pillar[5]arene with 10 allyl groups formed 1:1 complexes featuring a one-dimensional (1D) channel structure. For pillar[5]arene bearing 10 benzyl groups, one molecule of n-hexane was located in the cavity of pillar[5]arene, and another n-hexane molecule was located outside of the cavity between two pillar[5]arenes. The substituent-dependent differences in molecular arrangement influenced the uptake, release, and molecular dynamics of the n-hexane guest. The substituent effects were not observed in host–guest chemistry in solution, and these features are unique for the crystal state host–guest chemistry of pillar[5]arenes.     

Cucurbit[7]uril complexations of bis(isoquinolinium)alkane dications in aqueous solution

The 1:1 and 2:1 host–guest complexation of a series of 1,n-bis(isoquinolinium)alkane dications (Iq(CH₂)_nIq²⁺, n = 2, 4, 5, 6, 8, 9, 10 and 12, and Iq(p-xylene)Iq²⁺) by cucurbit[7]uril (CB[7]) in aqueous solution has been investigated by ¹H NMR spectroscopy and ESI mass spectrometry. The site of binding of the first CB[7] is dependent on the nature of the central linker group, with encapsulation of the p-xylene group or the polymethylene chain when n = 6–10.With shorter (n = 2–5) or longer (n = 12) chains, the first CB[7] binds over an isoquinolinium group. With a second CB[7], the binding of the central group is abandoned in favour of the CB[7] hosts encapsulating the two cationic isoquinolinium termini. The 1:1 and 2:1 host–guest stability constants are related to modes of binding and the nature of the central linkers, and are compared with dicationic guests bearing different terminal groups.     

Host Perturbation in a β‐Hydroquinone Clathrate Studied by Combined X‐ray/Neutron Charge‐Density Analysis: Implications for Molecular Inclusion in Supramolecular Entities

X‐ray/neutron (X/N) diffraction data measured at very low temperature (15 K) in conjunction with ab initio theoretical calculations were used to model the crystal charge density (CD) of the host–guest complex of hydroquinone (HQ) and acetonitrile. Due to pseudosymmetry, information about the ordering of the acetonitrile molecules within the HQ cavities is present only in almost extinct, very weak diffraction data, which cannot be measured with sufficient accuracy even by using the brightest X‐ray and neutron sources available, and the CD model of the guest molecule was ultimately based on theoretical calculations. On the other hand, the CD of the HQ host structure is well determined by the experimental data. The neutron diffraction data provide hydrogen anisotropic thermal parameters and positions, which are important to obtain a reliable CD for this light‐atom‐only crystal. Atomic displacement parameters obtained independently from the X‐ray and neutron diffraction data show excellent agreement with a |ΔU| value of 0.00058 Ų indicating outstanding data quality. The CD and especially the derived electrostatic properties clearly reveal increased polarization of the HQ molecules in the host–guest complex compared with the HQ molecules in the empty HQ apohost crystal structure. It was found that the origin of the increased polarization is inclusion of the acetonitrile molecule, whereas the change in geometry of the HQ host structure following inclusion of the guest has very little effect on the electrostatic potential. The fact that guest inclusion has a profound effect on the electrostatic potential suggests that nonpolarizable force fields may be unsuitable for molecular dynamics simulations of host–guest interaction (e.g., in protein–drug complexes), at least for polar molecules.     

Complexation of N-methyl-4-(p-methyl benzoyl)-pyridinium methyl cation and its neutral analogue by cucurbit[7]uril and β-cyclodextrin: a computational study

In this work, molecular dynamics (MD) simulations have been conducted to study the inclusion complexes between cucurbit[7]uril (CB7) and β-cyclodextrin (β-CD) with N-methyl-4-(p-methyl benzoyl)-pyridinium methyl cation, and N-methyl-4-(p-methyl benzoyl)-pyridine in aqueous solutions to gain detailed information about the dynamics and mechanism of the inclusion complexes. The obtained MD trajectories were used to estimate the binding free energy of the studied complexes using the molecular mechanics/Poisson Bolzmann surface area (MM–PBSA) method. Results indicate preference of CB7 to bind to the cationic guest more than the neutral guest, whereas β-CD exhibits more or less the same affinity to complex with either species. Furthermore it was interesting to note that β-CD forms more stable complexes with both guests than CB7. Average structure of each complex and the distances between the center of masses of the guest and the host were also discussed.     

Atom-atom potential analysis of the complexing characteristics of cyclodextrins (host) with benzene and p-dihalobenzenes (guest)

Abstract

Intermolecular interaction and modelling calculations on the complexes of α-, β- and γ-cyclodextrins (host) with benzene and p-dihalobenzenes (guest) were performed. The complex formation mechanism between the host and guest molecules was evaluated from three-dimensional potential maps generated by the atom-atom potential method, and the molecular packing of the complexed compounds was visualized by a space-fill representation. Stable inclusion complexes only form when both the host and guest molecules experience a significant decrease in the complexing potential. The host and guest molecules have a maximum molecular surface contact at the minimum potential, which depends on both the cavity size and the molecular volumes of the guest molecules. The calculated interaction energies can be correlated to the association constants of complex formation determined from experiment. The molecular dynamics of the guest molecules are also discussed.     

Triple Emission from p‐Dimethylaminobenzonitrile–Cucurbit[8]uril Triggers the Elusive Excimer Emission

The intriguing dual‐emission behavior of p‐ dimethylaminobenzonitrile (DMABN) and the identity of the associated excited states is, arguably, the most extensively investigated and also controversially discussed molecule‐ specific phenomenon of modern photochemistry. We have now found a new, third fluorescence band when DMABN is encapsulated within the water‐soluble molecular container cucurbit[8]uril (CB8). It is centered between the previously observed emissions and assigned to the elusive excimer emission from DMABN through 1:2 CB8:DMABN complex formation. Heating of the CB8 ? (DMABN)₂ complex from 0 to 100 °C results in the dissociation of the ternary complex and restoration of the dual‐emission properties of the monomer. Alternatively, monomer emission can be obtained by selecting cucurbit[7]uril (CB7), a host homologue that is too small to accommodate two DMABN molecules, or by introducing ethyl instead of methyl groups at the amino terminus of the aminobenzonitrile guest.     

Experiments on moving interaction boundaries and their characteristics of focusing and probing of both guest and host target molecules

In this paper, the concept of a moving interaction boundary (MIB) is proposed with regard to guest and host molecules. With 2-naphthalene-sulfonate (2-NS) and β-cyclodextrin (CD) as the model guest and host compounds, respectively, the relevant experiments were carried out on the MIB in capillary electrophoresis (CE). The experiments show that (1) there are a MIB and a complex boundary (CB) if proper guest and host molecules are used; (2) the MIB system has the characteristic of selective focusing and probing of the target 2-NS; (3) the system also has the characteristic of selective probing of the target host molecule β-CD without UV-absorbance, making the direct UV determination of β-CD from other CDs possible; (4) interestingly, the focusing of the guest molecule is a kind of leaky-sample stacking rather than a collection of analytes in sample sweeping; (5) the mechanism of MIB-induced separation of target analyte from unwanted ones is similar to but different from that of an affinity chromatography. In addition, the utility of MIB was briefly tested for a real sample of wastewater spiked with 2-NS.     

Transformative Supramolecular Vesicles Based on Acid-Degradable Acyclic Cucurbit[n]uril and a Prodrug for Promoted Tumoral-Cell Uptake

Smart supramolecular vesicles constructed by host–guest interactions between “acid-degradable” acyclic cucurbit[n]uril (CB[n]) and a doxorubicin prodrug are reported. “Acid-degradable” acyclic CB[n] is a high-affinity host for several common antitumor drugs, and its degradation leads to a more dramatic decrease in binding affinity than that observed for “acid-sensitive” hosts. Supramolecular complexation between acid-degradable acyclic CB[n] and a doxorubicin prodrug resulted in the formation of negatively charged supramolecular vesicles. The prodrug strategy allowed doxorubicin to be conjugated to vesicles in a stable manner with a high drug-loading ratio of 20 %. The resulting supramolecular vesicles were responsive to tumor acidity (pH 6.5). Induced by mildly acidic conditions (pH 6.5–5.5), acid-degradable acyclic CB[n] could be degraded, and this led to a vesicle-to-micelle transition to form positively charged micelles. This transition resulted in a pH-dependent change in size and surface charge, which improved tumoral-cell uptake for doxorubicin.