A triply-responsive supramolecular amphiphile fabricated by a thermal-responsive pillar[5]arene-based host–guest recognition motif

A novel molecular recognition motif was built between a neutral water soluble pillar[5]arene and decyltrimethylammonium bromide in water. Its thermal-controlled complexation with G1 in water was investigated. Furthermore, based on this new thermal responsive host–guest recognition motif, we further constructed a supramolecular amphiphile between this pillar[5]arene and a trimethylammonium bromide derivative containing an azobenzene group at the other end. This supramolecular amphiphile showed triply-responsiveness, that is, thermal responsiveness of the host–guest complex, photo-responsiveness of the azobenzene group and chemical-responsiveness by adding β-CD.     

A supramolecular polymer network constructed by pillar[5]arene-based host–guest interactions and its application in nitro explosive detection

Journal of Inclusion Phenomena and Macrocyclic Chemistry - The development of reliable methods for the rapid and selective detection of nitro-explosive were vital concern for national security due...     

Efficient enhancement of fluorescence emission via TPE functionalized cationic pillar[5]arene-based host–guest recognition-mediated supramolecular self-assembly

A tetraphenylethene (TPE) functionalized cationic pillar[5]arene (CWP5-TPE) was successfully synthesized, and the intramolecular rotation of the TPE motif was restricted via cationic pillar[5]arene-based host–guest recognition-mediated supramolecular self-assembly in water, resulting in the efficient enhancement of fluorescence emission based on the aggregation induced emission (AIE) mechanism. CWP5-TPE self-assembled into nanoribbons while the host–guest inclusion complex formed into supramolecular amphiphile nanoparticles in water.     

Functioning via host–guest interactions

Molecular recognition is essential for realizing functional supramolecular materials. Non-covalent host–guest interactions are an effective tool to introduce switching and functional properties into materials. This review focuses on the achievement of selective molecular adhesion, self-healing, toughness, and actuation properties. These functions have been achieved by reversible bond formation with cyclodextrins (CDs). Self-healing materials with host–guest interactions involving CDs have been used to achieve redox-responsive healing properties and healing efficiency. Furthermore, the materials, which undergo self-healing by chemical and physical mechanisms, exhibit rapid and efficient self-healing properties under semi-dry conditions. To prepare a supramolecular actuator using host–guest complexes, two approaches have been introduced. The first is the functionalization of a supramolecular gel actuator by changing the cross-linking density, and the second is the functionalization of a topological gel actuator by changing distances between the cross-linking points. Both actuators exhibit contractive bending behavior. This review summarizes advancements within the past ten years in supramolecular materials that function via the chemical mechanism of host–guest interactions and the physical mechanism of the sliding motion of ring molecules.     

Proton transfer-assisted host–guest complexation between a difunctional pillar[5]arene and amine-based guests

Proton transfer from a difunctional pillar[5]arene containing two carboxylic acid moieties to amine-based guests occurs in the host–guest complexation. The binding affinities are enhanced effectively due to the existence of electrostatic interactions.     

Solubility enhancement of kinetin through host–guest interactions with cucurbiturils

We explored the use of cucurbiturils to form inclusion complexes to overcome the solubility problems of kinetin, a plant cytokinin. Inclusion complexes between kinetin and Q[7], TMeQ[6] and HMeQ[6] in aqueous solution and in solid state were investigated by phase solubility studies, ¹H NMR and IR. The effects of pH and temperature on complex stability were also investigated. Phase solubility studies showed that kinetin solubility increased in a linear fashion as a function of Q[7] and TMeQ[6] concentrations. However, kinetin solubility increased first, then decreased as the HMeQ[6] concentration increased, and the maximum solubility of kinetin was achieved at 4.95 mM in HMeQ[6]. The solubility of kinetin as well as the stability constant of its complex with Q[7] were affected by the pH of the medium. The thermodynamic parameters of the complex formation were also determined, and it showed that the formation of the inclusion complexes between kinetin and Q[7] was enthalpy controlled, suggesting that hydrophobic and van der Waals interactions were the main driving forces. Moreover, we found that the size of the cavity of cucurbituril played an important role in the association process. The formation of inclusion complexes between Q[7], TMeQ[6] and HMeQ[6] with kinetin was confirmed by ¹H NMR, and IR spectroscopy showed the presence of inclusion complexes in solid state. Our results demonstrated that the complexation of kinetin with Q[n] could be used to improve the solubility of kinetin in aqueous solution.     

Influence of self-assembly of amphiphilic imidazolium ionic liquids on their host–guest complexes with cucurbit[n]urils

Two symmetric amphiphilic imidazolium ionic liquids having ω-undecenyl chains form supramolecular complexes with CB[7] and CB[8] in water as revealed by ¹H NMR spectroscopy and MALDI-MS. Binding constants in the range 10⁴ to 10⁵ M^?1 were estimated from the conductivity measurements for the 1:1 complexes of these imidazolium ionic liquids with CB[7] and CB[8]. Radical initiated polymerization of these host–guest complexes at concentrations above the critical self-assembly concentration of imidazolium ionic liquids to form liposomes, destroys completely (CB[7]) or partially (CB[8]) the host–guest ionic liquid@CB[n] complex; this behaviour was proved by titration with acridine orange tricyclic dye, of CB[n]s in the colloidal solutions of the liposomes before and after performing dialysis to remove free CB[n]s. Thus, the increase in the fluorescence emission of acridine orange by CB[7] is not observed if the polymerized ionic liquid@CB[7] complex is submitted to dialysis to remove uncomplexed CB[7]. Analogous study by titration of absorbance change of acridine orange solutions caused by CB[8], reveals only a partial destruction of the host–guest complex by self-assembly of amphiphilic ionic liquid above the critical self-assembly concentration. The results obtained have been rationalized considering that the driving force for the formation of supramolecular ionic liquid@CB[n] complexes is a hydrophobic interaction between the apolar alkenyl chain and the cucurbituril interior cavity and that these hydrophobic interactions are disturbed when self-assembly leading to liposomes occurs.     

Stimuli-responsive polymeric materials functioning via host–guest interactions

Molecular recognition is essential for realizing functional supramolecular materials. Non-covalent host–guest interactions are an effective tool to introduce switching and functional properties into materials. This review focuses on the achievement of selective molecular adhesion, self-healing, toughness, and actuation properties. These functions have been achieved by reversible bond formation with cyclodextrins (CDs). Self-healing materials with host–guest interactions involving CDs have been used to achieve redox-responsive healing properties and healing efficiency. Furthermore, the materials, which undergo self-healing by chemical and physical mechanisms, exhibit rapid and efficient self-healing properties under semi-dry conditions. To prepare a supramolecular actuator using host–guest complexes, two approaches have been introduced. The first is the functionalization of a supramolecular gel actuator by changing the cross-linking density, and the second is the functionalization of a topological gel actuator by changing distances between the cross-linking points. Both actuators exhibit contractive bending behavior. This review summarizes advancements within the past 10 years in supramolecular materials that function via the chemical mechanism of host–guest interactions and the physical mechanism of the sliding motion of ring molecules.     

Protein stabilization through supramolecular host–guest interactions with cyclodextrin-modified nanoparticles

This study demonstrates the protein stabilization of gelatin through supramolecular interactions of silica nanoparticles and the influence on the point of denaturation. The phenomenon was studied in diluted solutions by dynamic light scattering, viscosity measurements, and differential scanning calorimetry. Native gelatin is stabilized by cyclodextrin functionalized SiO₂ nanoparticles. After heating, increased supramolecular interactions of the nanoparticles with the denaturated gelatin coils are observed by progressive agglomeration. The described observation also resulted in a melting temperature shift from 30 °C, for native gelatin, to about 47 °C for the gelatin/CD-SiO₂, which indicates the supramolecular stabilization of the gelatin chain structure. It was found that the gelatin is supramolecularly immobilized on the nanoparticle up to a certain temperature through complexation by cyclodextrin. The described results, also confirmed by DSC and viscosity measurements, show the prospect of using cyclodextrin-modified surfaces for the immobilization of the proteins.     

A cationic water-soluble pillar[7]arene: Synthesis and its fluorescent host−guest complex in water

The first cationic water-soluble pillar[7]arene CWP7 was prepared. ¹H NMR, ¹³C NMR, and MALDI-TOF-MS were performed to provide converging evidences of the structure of obtained CWP7. Host–guest complexation between this novel pillar[7]arene-based host and sodium pyren-1-olate guest G was fully investigated in aqueous solution. Increased fluorescence intensity was observed during the inclusion complexation. Driven by the cooperativity of electrostatic interactions, π-stacking interactions and hydrophilic/hydrophobic interactions, the guest penetrated into the cavity of CWP7 to form a pseudorotaxane-type inclusion complex with relatively high binding affinity.     

Succinyl-β-cyclodextrin–driven synthesis of a nitrogen-fused five-ring heterocycle using GBB-based [4 + 1] cycloaddition via supramolecular host–guest interactions

We synthesized a mono-succinyl-β-cyclodextrin (Suc-β-CD) and used it as a supramolecular organic acid catalyst for the synthesis of the therapeutically relevant indazolo[3′,2':2,3]imidazo[1,5-c]quinazolin-6(5H)-one (IIQ) via the Groebke–Blackburn–Bienaymé reaction (GBB). The Suc-β-CD was characterized using MALDI-TOF mass spectrometry, NMR spectroscopy, FT-IR spectroscopy, and SEM. A possible reaction mechanism via molecular complexation is suggested, based on 2D NMR (ROESY) spectroscopy, FT-IR spectroscopy, FE-SEM, and DSC analysis. The significant advantages of this atom-economical method include the simple single-step preparation of the catalyst, tolerance of a wide range of functional groups, easy catalyst recyclability, and absence of a tedious workup or purification; moreover, this method eschews the use of hazardous reagents/solvents.     

Host−guest inclusion systems of nicotine with acyclic cucurbit[n]urils for controlled heat releases

Journal of Inclusion Phenomena and Macrocyclic Chemistry - The thermal stability and slow release of nicotine are crucial to its shelf-life and applications. In this article, three kinds of acyclic...     

Simultaneous enhancement of phosphorescence and chirality by host–guest recognition of molecular tweezers

A novel type of host–guest recognition systems have been developed on the basis of a Au(III) molecular tweezer receptor and chiral Pt(II) guests. The complementary host–guest motifs display high non-covalent binding affinity (K_a: ～10⁴ L/mol) due to the participation of two-fold intermolecular π–π stacking interactions. Both phosphorescence and chirality signals of the Pt(II) guests strengthen in the resulting host–guest complexes, because of the cooperative rigidifying and shielding effects rendered by the tweezer receptor. Their intensities can be reversibly switched toward pH changes, by taking advantage of the electronic repulsion effect between the protonated form of tweezer receptor and the positive-charged guests in acidic environments. Overall, the current study demonstrates the feasibility to enhance and modulate phosphorescence and chirality signals simultaneously via molecular tweezer-based host–guest recognition.     

Supramolecular architectures of metal–organic host–guest compounds

Metal?Corganic frameworks are a class of materials with new and interesting properties (Angew Chem Int Ed 43:2334, 2004; Coorg Chem Rev 38:1213, 2009; Adv Mater 23:249, 2011). In particular, porous metal organic systems are attracting considerable interest because of their potential use as sensors, catalysts and, in general, in host?Cguest chemistry (Acc Chem Res 43:1115, 2010). The so-called ??wheel and axle?? compounds play an important role in the developing of supramolecular chemistry and there are a lot of studies dealing with their inclusion properties and host?Cguest chemistry (Comprehensive supramolecular chemistry, 1996). Classical ??wheel and axle?? molecules have a long, thin, central part (the axle) with two bulky ends (the wheels). Here, new compounds with host properties are described, that we called ??wheel and axle metal?Corganic?? diols (WAMOD), that are decorated with OH groups in the wheel. In particular, their clathration properties are discussed in connection with their crystal structures. A modular strategy is applied to obtain WAMODs: coordination chemistry is used together with soft interactions (H-bond, ?ШC?? interaction), with the aim to realize a dynamic framework that is able to reversibly capture and release a guest. The coordination bond is robust and permits to obtain WAMODs with different arrangements of the axle; the hydrogen bonds and/or the other soft interactions are responsible for the thin adjustments in the crystal packing that allow reversible adsorption/desorption of the guest.     

Host–guest complexes of various cucurbit[n]urils with the hydrochloride salt of 2,4-diaminoazobenzene

The interaction products of normal cucurbit[n]urils (n = 7, 8; Q[7] Q[8]) and a sym- tetramethyl-substituted cucurbit[6]uril derivative (TMeQ[6]) with the hydrochloride salts of 2,4-diaminoazobenzene (g·HCl) were investigated in aqueous solution using ¹H NMR spectroscopy, electronic absorption spectroscopy, as well as single crystal X-ray diffraction. The ¹H NMR spectra analysis established a basic interaction model in which inclusion complexes with a host:guest ratio of 1:1 form for the TMeQ[6] and Q[7] cases, while they form with a host:guest ratio of 1:2 for the Q[8] case. Commonly, the hosts selectively bound to the phenyl moieties of the guests. Absorption spectrophotometric analysis in aqueous solution defined the stability of the host–guest inclusion complexes at pH 3.2. Quantitatively, at this pH, complexes with a host:guest ratio of 1:1—those with smaller hosts TMeQ[6] and Q[7]—formed with logK values between 6 and 7. That with host Q[8] and a host:guest ratio of 1:2 formed with a logK value of 10.8. Single crystal X-ray structures of the inclusion complexes TMeQ[6]–g·HCl and Q[8]–g·HCl showed the phenyl moiety of the guest inserted into the host cavity. This result supports the solution-based ¹H NMR spectroscopic study.     

Host–guest interactions of a twisted cucurbit[15]uril with paraquat derivatives and bispyridinium salts

Host–guest complexations of a twisted cucurbit[15]uril with some paraquat derivatives and bispyridinium salts in aqueous solution are investigated by nuclear magnetic resonance, UV–vis spectrometry and isothermal titration calorimetry. These complexations are mainly enthalpy-driven.     

Supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host–guest interactions

Supramolecular polymers constructed by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host-guest interactions have received increasing attention due to their elegant structures,outstanding properties,and potential applications.Hydrogen bonding endows these supramolecular polymers with good adaptability and reversibility,while macrocyclic host-guest interactions give them good selectivity and versatile stimuli-responsiveness.Therefore,functional supramolecular polymers fabricated by these two highly specific,noninterfering interactions in an orthogonal way have shown wide applications in the fields of molecular machines,electronics,soft materials,etc.In this review,we discuss the recent advances of functional supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydroge n bonding and host-guest interactions.In particular,we focus on crown ether-and pillar[n]arene-based supramolecular polymers due to their compatibility with multiple hydrogen bonds in organic solution.The fabrication strategies,interesting properties,and potential applications of these advanced supramolecular materials are mainly concerned.