Supramolecular Host-guest Chemistry Research Articles

Photochemical Design of Stimuli-Responsive Nanoparticles Prepared by Supramolecular Host–Guest Chemistry

We introduce the design of a thermoresponsive nanoparticle via sacrificial micelle formation based on supramolecular host–guest chemistry. Reversible addition–fragmentation chain transfer (RAFT) polymerization was employed to synthesize well-defined polymer blocks of poly(N,N-dimethylacrylamide) (poly(DMAAm)) (Mn,SEC = 10 700 g mol–1, Đ = 1.3) and poly(N-isopropylacrylamide) (poly(NiPAAm)) (Mn,SEC = 39 700 g mol–1, Đ = 1.2), carrying supramolecular recognition units at the chain termini. Further, 2-methoxy-6-methylbenzaldehyde moieties (photoenols, PE) were statistically incorporated into the backbone of the poly(NiPAAm) block as photoactive cross-linking units. Host–guest interactions of adamantane (Ada) (at the terminus of the poly(NiPAAm/PE) chain) and β-cyclodextrin (CD) (attached to the poly(DMAAm chain end) result in a supramolecular diblock copolymer. In aqueous solution, the diblock copolymer undergoes micellization when heated above the lower critical solution temperature (LCST) of the thermoresponsive poly(NiPAAm/PE) chain, forming the core of the micelle. Via the addition of a 4-arm maleimide cross-linker and irradiation with UV light, the micelle is cross-linked in its core via the photoinduced Diels–Alder reaction of maleimide and PE units. The adamantyl–cyclodextrin linkage is subsequently cleaved by the destruction of the β-CD, affording narrowly distributed thermoresponsive nanoparticles with a trigger temperature close to 30 °C. Polymer chain analysis was performed via size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and dynamic light scattering (DLS). The size and thermoresponsive behavior of the micelles and nanoparticles were investigated via DLS as well as atomic force microscopy (AFM).

Host–guest supramolecular chemistry in solid-state nanopores: potassium-driven modulation of ionic transport in nanofluidic diodes

We describe the use of asymmetric nanopores decorated with crown ethers for constructing robust signal-responsive chemical devices. The modification of single conical nanopores with 18-crown-6 units led to a nanodevice whose electronic readout, derived from the transmembrane ion current, can be finely tuned over a wide range of K(+) concentrations. The electrostatic characteristics of the nanopore environment arising from host-guest ion-recognition processes taking place on the pore walls are responsible for tuning the transmembrane ionic transport and the rectification properties of the pore. This work illustrates the potential and versatility of host-guest chemistry, in combination with nanofluidic elements, as a key enabler to achieve addressable chemical nanodevices mimicking the ion transport properties and gating functions of specific biological channels.

Interfacial assembly of dendritic microcapsules with host-guest chemistry.

The self-assembly of nanoscale materials to form hierarchically ordered structures promises new opportunities in drug delivery, as well as magnetic materials and devices. Herein, we report a simple means to promote the self-assembly of two polymers with functional groups at a water-chloroform interface using microfluidic technology. Two polymeric layers can be assembled and disassembled at the droplet interface using the efficiency of cucurbit[8]uril (CB[8]) host-guest supramolecular chemistry. The microcapsules produced are extremely monodisperse in size and can encapsulate target molecules in a robust, well-defined manner. In addition, we exploit a dendritic copolymer architecture to trap a small hydrophilic molecule in the microcapsule skin as cargo. This demonstrates not only the ability to encapsulate small molecules but also the ability to orthogonally store both hydrophilic and hydrophobic cargos within a single microcapsule. The interfacially assembled supramolecular microcapsules can benefit from the diversity of polymeric materials, allowing for fine control over the microcapsule properties.

The impact of pressure on β-Cyclodextrin·acetaminophen inclusion complexes

Cyclodextrins (CDs) have attracted considerable interest as model systems in supramolecular host-guest chemistry. They are described as hollow truncated cones with a hydrophilic outer surface and a nonpolar inner cavity suitable for small molecules' encapsulation.[1] By virtue of their character, CDs are used as excipients to improve the aqueous solubility of active pharmaceutical ingredients (APIs). High-pressure crystallisation techniques have been established as a suitable tool for exploring the phenomenon of polymorphism and solvate formation of pharmaceutical compounds throughout numerous examples reported in the literature.[2] Thus, exploring the inclusion-complex formation and the polymorphic behaviour of CDs with APIs at high pressure would be an interesting extension of the technique. The present work describes the attempt of an in-situ crystallisation of β-CD·acetaminophen inclusion complex and compression studies of the known β-CD·acetaminophen complex[3] in different crystallisation media at pressures up to 1.0 GPa. A new high-pressure crystal form observed at 0.8 GPa as well as unexpected results are presented herein. The crystals have been characterised by means of polarised optical microscopy, Raman spectroscopy and single-crystal X-ray diffraction using both home and synchrotron sources.

Solvent- and guest-responsive supramolecular self-assembly of 1,3,5-tris(10-carboxydecyloxy) benzene by scanning tunneling microscopy

• TCDB can entrap solvent molecules or π-electron-conjugated guest molecules. • We calculate hydrogen bonding which is crucial to stabilize the assembly networks. • Structural properties rely on the solvent- and guest-responsive assembly. • Kinetics and thermodynamics explain the morphology character of polarity. Two-dimensional hydrogen-bonded networks formed in the self-assembly of 1,3,5-tris(10-carboxydecyloxy) benzene (TCDB) show regular solvent- and guest-induced supramolecular structural properties, which have been presented by scanning tunneling microscopy at the liquid–solid interface at ambient conditions. TCDB acting as a host template can entrap solvent molecules or π-electron-conjugated guest molecules to fabricate the flexible co-adsorption architectures, which are subject to the balance between the hydrogen bonding of the host lattice and the van der Waals forces between the host and the guest molecules. Hydrogen bonding among TCDB molecules is crucial to stabilize the host networks to settle the system into a global minimum of Gibbs free energy. We also find a strong correlation between the structural parameters and the physical properties of the solvent. Statistical analysis shows that the unit cell volume of TCDB dissolved in nonpolar 1-phenylotane and n -tetradecane shrank significantly compared with that of host–guest system, which fully reflects the coadsorption effect of nonpolar solvent molecules. Our results identify that the kinetic effect of adsorption/desorption as well as the solvent viscosity comes into play in tuning the two-dimensional self-assembled structures. Furthermore, mechanical calculations demonstrate that TCDB incline to adsorb with a larger dipole configuration in nonpolar solvents due to its dissolvability. It is believed that the results are of significance to supramolecular host–guest chemistry and surface science.

Two-dimensional self-assemblies of telechelic organic compounds: structure and surface host–guest chemistry

Guiding the self-assembly of different types of functional molecules into well-defined structures on surfaces is beneficial for both fundamental surface and interface study and emerging application fields, especially molecular and organic electronics. This review focuses on understanding the two-dimensional self-assembly process of telechelic organics, which feature alkoxylene chains terminated with carboxyl groups. With the combined flexibility of alkyl chains and directionality of carboxyl groups, telechelic organics show unique assembly behaviour on two-dimensional surfaces. By increasing the length of the alkoxylene chains, the cavities in the nanoporous networks of telechelic trimesic acid (1,3,5-benzene tricarboxylic acid) derivatives change from hexagonal cavities to irregular cavities on a highly oriented pyrolytic graphite surface. The nanoporous networks provide a flexible host template for host-guest supramolecular chemistry because the cavities framed by the flexible alkoxylene chains can be changed in accordance with the sizes/shapes of the guest molecules. Furthermore, the terminal carboxylic group can form a hydrogen bond with another hydrogen bond partner, leading to multi-component structural motifs and hierarchical assemblies. The unique assembly behaviour of telechelic organics makes them promising structures as important building blocks for the design and construction of complex self-assembled nanoarchitectures.

Host-guest supramolecular chemistry at solid-liquid interface: An important strategy for preparing two-dimensional functional nanostructures

Supramolecular self-assembly, an important strategy in nanotechnology, has been widely studied in the past two decades. In this review, we have introduced the recent progress on construction of two-dimensional (2D) nanostructures by host-guest supramolecular chemistry at solid-liquid interface, and the interactions between the host assembly and the guest molecules are the major concerns. At first, the hydrogen bonds connected hybrid structures are discussed. And then we have paid a close attention on the surface-confined condensation reactions that has flourished recently in direct preparing novel nanostructures with increasing structural complexity. In the end, the cavity confinement of the 2D supramolecular host-guest architectures has been studied. On the basis of the above-mentioned interactions, a group of functional hybrid structures have been prepared. Notably, scanning tunneling microscopy (STM), a unique technique to probe the surface morphology and information at the single molecule level, has been used to probe the formed structures on highly oriented pyrolytic graphite (HOPG) surface.

ChemInform Abstract: Construction of Two‐Dimensional (2D) H‐Bonded Supramolecular Nanostructures Studied by STM

AbstractReview: 42 refs.

An Easy and Multigram-Scale Synthesis of Pillar[5]quinone by the Hypervalent Iodine Oxidation of 1,4-Dimethoxypillar[5]arene

Pillar[5]quinone (P[5]Q), a potential molecule for anion recognition and supramolecular host-guest chemistry, has not as yet been used for practical purposes, presumably due to the synthetic difficulties in obtaining it in large amounts. Herein, we reveal an easy-to-operate and chromatography-free synthetic strategy that can furnish P[5]Q on a multigram scale; its success relies on the utility of hypervalent iodine, generated in situ from Oxone/iodobenzene, as an efficient oxidant. Pillar[5]quinone was obtained in multigram quantities by oxidation of 1,4-dimethoxypillar[5]arene with Oxone/iodobenzene and simple purification by crystallization from 1,1,2,2-tetrachloroethane, thus opening up the opportunity to explore the properties of this interesting macrocyclic quinone.

Construction of two-dimensional (2D) H-bonded supramolecular nanostructures studied by STM

Abstract In this review, a group of two-dimensional (2D) hydrogen-bonded supramolecular networks developed in our laboratory are discussed. Our attention is mainly focused on: (1) recognition of Fe3+ through two-component molecular networks; (2) site-selective fabrication of 2D fullerene arrays; and (3) fabrication of the nanoporous structure regulated by photoisomerization reaction process. It is envisioned that special supramolecular nanostructures, through H-bonding interactions, can be constructed or reconstructed to be further investigated toward the research of multi-component systems, molecule recognition, single molecular switches, and host–guest supramolecular chemistry.

Molecular templates and nano-reactors: two-dimensional hydrogen bonded supramolecular networks on solid/liquid interfaces

With tunable cavities, the two-dimensional (2D) hydrogen bonded supramolecular networks are receiving increasing attention in surface supramolecular chemistry during the past decade. Herein, we give a brief account of our efforts on the 2D supramolecular host–guest chemistry based on molecular networks connected by hydrogen bonds, with an aid of scanning tunnelling microscopy (STM) technique. Following the molecular assembling, we have constructed a group of two-dimensional H-bonded supramolecular networks with cavities of different sizes, shapes, and symmetry characteristics on HOPG surface. Our researches have reported that these open porous structures could serve as molecular templates to host alien ensembles, as molecular sieves for molecular separation and recognition, as molecular sensors for ion detections, and as spatial confiners to control chemical reactions. It can be noticed that the interactions between host templates and guest molecules are emphasized throughout this review. On the basis of the confinement of supramolecular networks, it could be less problematic to explore the controllability, predictability, stability and applicability of the ordered structures.

Supramolecular Host-Guest Asymmetric Induction In Organic Synthesis

In past decades, the pharmacopoeia was dominated by racemates, but since the emergence of new technologies in the 1990s that allowed the preparation of pure enantiomers in significant quantities, the awareness and interest in the stereochemistry of drug actions have increased. In this short review, the implementation of several hosts, guests, building blocks and methods in host-guest supramolecular chemistry was outlined with an emphasis on the synthetic aspects, catalyst libraries and molecular recognition. Solid-state host-guest interactions, intra- and intermolecular host-guest photoreactions in solution and in the solid state, molecular and supramolecular self-assembly and molecular recognition between host and guests, and some specific and important reactions, such as aldol and Michael reactions, were reviewed. Keywords: Asymmetric, catalyst libraries, chiral auxiliary, combinatorial chemistry, host-guest, photochirogenesis, self-assembly, supramolecular

Oligoether-strapped meso-pyrimidinylporphyrins

Bis(oligoether-strapped) zinc(II)-meso-pyrimidinylporphyrins were readily synthesized via nucleophilic aromatic substitution reactions of biscathechol-substituted tri- or tetraethylene glycol straps on the upper and lower faces of a Zn(II)-A2B2-meso-dichloropyrimidinylporphyrin precursor. The crown ether-like bridges surrounding the porphyrin core create peculiar cavities above and below the macrocyclic plane with appealing features for supramolecular host–guest chemistry.

ChemInform Abstract: Self‐Assembled Supramolecular Networks at Interfaces: Molecular Immobilization and Recognition Using Nanoporous Templates

AbstractReview: 40 refs.

High-Resolution Rotational Spectroscopy of a Cyclic Ether.

The conformational landscape of crown ethers has constituted a central topic in the development of host-guest supramolecular chemistry. We report a high-resolution rotational study of a crown ether, 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5), by means of molecular beam Fourier transform microwave spectroscopy. The considerable size and the broad range of conformations allowed by the flexibility of the cyclic backbone of this ether pose important challenges to spectroscopy approaches. In this investigation, three stable rotamers of the 15-crown-5 ether have been identified and characterized through their rotational constants and centrifugal distortion coefficients. Ab initio quantum calculations at the MP2 level predict these conformers as the most stable ones for the title system and reproduce accurately their distinct structural features. The results pave the ground for an extensive survey of the conformational landscape of the 15-crown-5 and related cyclic ethers in the near term.

One-Pot Endgroup-Modification of Hydrophobic RAFT Polymers with Cyclodextrin by Thiol-ene Chemistry and the Subsequent Formation of Dynamic Core–Shell Nanoparticles Using Supramolecular Host–Guest Chemistry

Poly(methyl methacrylate) PMMA, synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization, was heated in a solvent at 100°C for 24 h leading to the loss of the RAFT endfunctionality and the complete conversion into a vinyl group. Mono(6-deoxy-6-mercapto)-β-cyclodextrin (β-CD-SH) was subsequently clicked onto the polymer by a thiol-ene reaction leading to PMMA with one β-CD as a terminal group (PMMA70–β-CD). Meanwhile, a RAFT agent with an adamantyl group has been prepared for the polymerization of 2-hydroxyethyl acrylate (HEA) leading to PHEA95–Ada. Two processes were employed to generate core–shell nanoparticles from these two polymers: a one-step approach that employs a solution of both polymers at stoichiometric amounts in DMF, followed by the addition of water, and a two step process that uses PMMA solid particles with surface enriched with β-CD in water, which have a strong tendency to aggregate, followed by the addition of PHEA95–Ada in water. Both pathways led to stable core–shell nanoparticles of ~150 nm in size. Addition of free β-CD competed with the polymer bound β-CD releasing the PHEA hairs from the particle surface. As a result, the PMMA particles started agglomerating resulting in a cloudy solution. A similar effect was observed when heating the solution. Since the equilibrium constant between β-CD and adamantane decreases with increasing temperature, the stabilizing PHEA chains cleaved from the surface and the solution turned cloudy due to the aggregation of the naked PMMA spheres. This process was reversible and with decreasing temperature the core–shell nanoparticles formed again leading to a clear solution.

Calixarene capped ZnS quantum dots as an optical nanoprobe for detection and determination of menadione

In this communication we report a p-sulfonatocalix[4]arene coated ZnS quantum dots "cup type" highly stable optical probe for the detection and determination of menadione (VK(3)) with high sensitivity and selectivity. The detection of VK(3) depends on supramolecular host-guest chemistry.

Nanoporous Carbohydrate Metal–Organic Frameworks

The binding of alkali and alkaline earth metal cations by macrocyclic and diazamacrobicyclic polyethers, composed of ordered arrays of hard oxygen (and nitrogen) donor atoms, underpinned the development of host-guest supramolecular chemistry in the 1970s and 1980s. The arrangement of -OCCO- and -OCCN- chelating units in these preorganized receptors, including, but not limited to, crown ethers and cryptands, is responsible for the very high binding constants observed for their complexes with Group IA and IIA cations. The cyclodextrins (CDs), cyclic oligosaccharides derived microbiologically from starch, also display this -OCCO- bidentate motif on both their primary and secondary faces. The self-assembly, in aqueous alcohol, of infinite networks of extended structures, which have been termed CD-MOFs, wherein γ-cyclodextrin (γ-CD) is linked by coordination to Group IA and IIA metal cations to form metal-organic frameworks (MOFs), is reported. CD-MOF-1 and CD-MOF-2, prepared on the gram-scale from KOH and RbOH, respectively, form body-centered cubic arrangements of (γ-CD)(6) cubes linked by eight-coordinate alkali metal cations. These cubic CD-MOFs are (i) stable to the removal of solvents, (ii) permanently porous, with surface areas of ~1200 m(2) g(-1), and (iii) capable of storing gases and small molecules within their pores. The fact that the -OCCO- moieties of γ-CD are not prearranged in a manner conducive to encapsulating single metal cations has led to our isolating other infinite frameworks, with different topologies, from salts of Na(+), Cs(+), and Sr(2+). This lack of preorganization is expressed emphatically in the case of Cs(+), where two polymorphs assemble under identical conditions. CD-MOF-3 has the cubic topology observed for CD-MOFs 1 and 2, while CD-MOF-4 displays a channel structure wherein γ-CD tori are perfectly stacked in one dimension in a manner reminiscent of the structures of some γ-CD solvates, but with added crystal stability imparted by metal-ion coordination. These new MOFs demonstrate that the CDs can indeed function as ligands for alkali and alkaline earth metal cations in a manner similar to that found with crown ethers. These inexpensive, green, nanoporous materials exhibit absorption properties which make them realistic candidates for commercial development, not least of all because edible derivatives, fit for human consumption, can be prepared entirely from food-grade ingredients.

Self-assembled supramolecular networks at interfaces: Molecular immobilization and recognition using nanoporous templates

In this review a series of organic-based open porous networks are discussed, in which hydrogen bonds play an important role in network formation. Using these open networks as molecular templates: 1) a wealth of functional guest species can be immobilized; 2) fullerene molecules can be separated and recognized; 3) photoisomerization reactions can be observed by STM; 4) 1D molecular arrays can be constructed; and 5) heterogeneous bilayer structures can be formed. It is envisioned that these supramolecular networks might be developed into a new family of useful soft frameworks for studies toward shape-selective catalysis, molecular recognition and host-guest supramolecular chemistry.

Homothiacalix[4]arenes: Synthetic Exploration and Solid‐State Structures

Homothiacalix[n]arenes have been largely underexposed compared with related (homo)heteracalixarenes, although their inherent structural features are particularly attractive for supramolecular host-guest chemistry. In this contribution, the synthetic macrocyclization protocols that afford homothiacalix[n]arenes have been reinvestigated and optimized, providing straightforward access to the parent homothiacalix[4]arene skeleton. Moreover, inner-rim (bis and tetrakis) ester functionalization and dimethylenethia bridge oxidation were successfully performed as well. Solution-phase (variable-temperature) NMR spectroscopy studies and solid-state X-ray structures provided complementary information on the conformational features of the novel macrocycles.