The role of chain length in cucurbit[8]uril complexation of methyl alkyl viologens

Viologens are among the most studied guests for cucurbit[8]uril (CB[8]) and their complexation is usually driven by bipyridyl core inclusion inside the cavity to maximize both hydrophobic and cation-dipole interactions. The presence of alkyl substituents on the guest alters this complexation mode, switching to aliphatic chain inclusion in U-folded conformation. Here we report a thorough study of the influence of the alkyl chain length on the binding mode of methyl alkyl viologens. The chain length of the studied guests was increased by two methylene groups starting from methyl dodecyl viologen (MVC12) to the octadecyl analogue (MVC18). Complexation in water, investigated by NMR spectroscopy and ITC, revealed a clear switch from 1:1 to 2:1 stoichiometry moving from 12 to 16 carbon atoms, as a consequence of the chain folding of the major portion of the longer alkyl chain in one CB[8] cavity and the inclusion of the full viologen unit by another host molecule. The CB[8]2•MVC18 complex crystal structure evidences the unprecedented 2:1 stoichiometry and quantified in 12 the number of carbon atoms necessary to fill the CB[8] cavity in U-shaped conformation

Cavitand Decorated Silica as a Selective Preconcentrator for BTEX Sensing in Air

The monitoring of benzene and other carcinogenic aromatic volatile compounds at the ppb level requires boosting both the selectivity and sensitivity of the corresponding sensors. A workable solution is the introduction in the devices of preconcentrator units containing molecular receptors. In particular, quinoxaline cavitands (QxCav) resulted in very efficient preconcentrator materials for the BTEX in air to the point that they have been successfully implemented in a com- mercial sensor. In this work, we report a highly efficient quinoxaline-based preconcentrator mate- rial, in which the intrinsic adsorption capacity of the QxCav has been maximized. The new material consists of silica particles covalently coated with a suitable functionalized QxCav derivative (QxCav@SiO2). In this way, all the cavities are exposed to the analyte flux, boosting the performance of the resulting preconcentration cartridge well above that of the pure QxCav. It is noteworthy that the preconcentrator adsorption capacity is independent of the relative humidity of the incoming air

The Origin of Selectivity in the Complexation of N-Methyl Amino Acids by Tetraphosphonate Cavitands

We report on the eligibility of tetraphosphonate resorcinarene cavitands for the molecular recognition of amino acids. We determined the crystal structure of 13 complexes of the tetraphosphonate cavitand Tiiii[H, CH3, CH3] with amino acids. 1H NMR and 31P NMR experiments and ITC analysis were performed to probe the binding between cavitand Tiiii[C3H7, CH3, C2H5] or the water-soluble counterpart Tiiii[C3H6Py+Cl-, CH3, C2H5] and a selection of representative amino acids. The reported studies and results allowed us (i) to highlight the noncovalent interactions involved in the binding event in each case; (ii) to investigate the ability of tetraphosphonate cavitand receptors to discriminate between the different amino acids; (iii) to calculate the Ka values of the different complexes formed and evaluate the thermodynamic parameters of the complexation process, dissecting the entropic and enthalpic contributions; and (iv) to determine the solvent influence on the complexation selectivity. By moving from methanol to water, the complexation changed from entropy driven to entropy opposed, leading to a drop of almost three orders in the magnitude of the Ka. However, this reduction in binding affinity is associated with a dramatic increase in selectivity, since in aqueous solutions only N-methylated amino acids are effectively recognized. The thermodynamic profile of the binding does not change in PBS solution. The pivotal role played by cation 12\u3c0 interactions is demonstrated by the linear correlation found between the log\u202fKa in methanol solution and the depth of +N\u2013CH3 cavity inclusion in the molecular structures. These findings are relevant for the potential use of phosphonate cavitands as synthetic receptors for the detection of epigenetic modifications of histones in physiological media

Phenoxy resin-based vinylogous urethane covalent adaptable networks

This work presents a post-polymerization approach to the preparation of vitrimers, exploiting the transamination of vinylogous urethane in linear phenoxy resins. Phenoxy vitrimers are obtained by a two-steps synthesis from a commercial phenoxy resin via partial conversion of hydroxyl groups to acetoacetates (AcAc), followed by network formation by reaction with m-xylylendiamine (XYDIA) as crosslinker. Three different vitrimers with variable crosslinking density are obtained by tuning the density of AcAc moieties along the phenoxy resin scaffold (5%, 10% and 15% conversion of hydroxyl groups). The conversion of linear polymers to dynamic crosslinked networks is confirmed by Dynamic Mechanical Thermal Analyzer (DMTA) and rheology measurements, followed by stress relaxation tests to investigate the kinetics of bond exchanges. Tensile tests as a function of reprocessing cycles reveal an increase of the maximum elongation and stress at break and prove the good recyclability of the vitrimers. Enhanced adhesive properties compared to pristine phenoxy resins are demonstrated, including the possibility to thermally re-join the assembly after its mechanical failure. Finally, the solvent-free preparation of vitrimer is explored for 5% crosslinked vitrimer via melt reactive blending, providing a valuable alternative to the less environmentally sustainable synthesis in solution

Hierarchical Self-assembly and Controlled Disassembly of a Cavitand-based Host-Guest Supramolecular Polymer

There is a considerable interest in dynamic materials featuring modular components with nano-scale dimensions and controlled responsiveness to external stimuli. Supramolecular polymers are a class of materials that fulfill nicely all these conditions. Here, we present a family of host-guest supramolecular polymers that combine the outstanding complexing properties of tetraphosphonate cavitands toward N-methylpyridinium guests with molecular switching. The designed monomer is a cavitand featuring four inward facing P=O groups at the upper rim and a single N-methylpyridinium unit at the lower rim, forming instantaneously a polymeric species in solution thanks to the high complexation constants measured for these host-guest interactions. This system has been analyzed by NMR spectroscopic and electrochemical techniques. In order to interpret the results of diffusion-sensitive experiments, we took advantage of the X-ray crystal structure obtained for the polymeric species and developed an original treatment of the PGSE data by non-linear fitting. The analysis of the experimental data identified an isodesmic polymerization model at monomer concentration below 20 mM, driven by intrachain host-guest interactions, and an additional level of tetrameric bundle aggregation above 20 mM, due to interchain dipolar and quadrupolar interactions. Two orthogonal disassembly procedures have been implemented: electrochemical reduction for the linear chains and solvent-driven dissolution for the bundles

Encapsulation of trimethine cyanine in cucurbit[8]uril: solution versus solid-state inclusion behavior

Inclusion of polymethine cyanine dyes in the cavity of macrocyclic receptors is an effective strategy to alter their absorption and emission behavior in aqueous solution. In this paper, the effect of the host-guest interaction between cucurbit[8]uril (CB[8]) and a model trimethine indocyanine (Cy3) on dye spectral properties and aggregation in water is investigated. Solution studies, performed by a combination of spectroscopic and calorimetric techniques, indicate that the addition of CB[8] disrupts Cy3 aggregates leading to the formation of a 1:1 host-guest complex with an association constant of 1.5 × 10 6 M -1 . At concentrations suitable for NMR experiments, the slow formation of a supramolecular polymer was observed, followed by precipitation. Single crystals X-ray structure elucidation confirmed the formation of a polymer with 1:1 stoichiometry in the solid state

Reusable Cavitand‐Based Electrospun Membranes for the Removal of Polycyclic Aromatic Hydrocarbons from Water

The removal of toxic and carcinogenic polycyclic aromatic hydrocarbons (PAHs) from water is one of the most intractable environmental problems nowadays, because of their resistance to remediation. This work introduces a highly efficient, regenerable membrane for the removal of PAHs from water, featuring excellent filter performance and pH-driven release, thanks to the integration of a cavitand receptor in electrospun polyacrylonitrile (PAN) fibers. The role of the cavitand receptor is to act as molecular gripper for the uptake/ release of PAHs. To this purpose, the deep cavity cavitand BenzoQxCav is designed and synthetized and its molecular structure is elucidated via X-Ray diffraction. The removal efficiency of the new adsorbent material toward the 16 priority PAHs is demonstrated via GC-MS analyses at ng L−1 concentration. A removal efficiency in the 32%, to 99% range is obtained. The regeneration of the membrane is performed by exploiting the pH-driven conformational switching of the cavitand between the vase form, where the PAHs uptake takes place, to the kite one, where the PAHs release occurs. The absorbance and regeneration capability of the membrane are successfully tested in four uptake/release cycles and the morphological stability

Triptycene-Roofed Quinoxaline Cavitands for the Supramolecular Detection of BTEX in Air

Two novel triptycene quinoxaline cavitands (DiTriptyQxCav and MonoTriptyQxCav) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the triptycene moieties at the upper rim of the tetraquinoxaline walls, promoting the confinement of the aromatic hydrocarbons within the cavity. The two cavitands were used as fiber coatings for solid-phase microextraction (SPME) BTEX monitoring in air. The best performances in terms of enrichment factors, selectivity, and LOD (limit of detection) values were obtained by using the DiTriptyQxCav coating. The corresponding SPME fiber was successfully tested under real urban monitoring conditions, outperforming the commercial divinylbenzene\u2013Carboxen\u2013polydimethylsiloxane (DVB\u2013CAR\u2013PDMS) fiber in BTEX adsorption

Selective discrimination and classification of G-quadruplex structures with a host–guest sensing array

The secondary structures of nucleic acids have an important influence on their cellular functions but can be difficult to identify and classify quickly. Here, we show that an arrayed suite of synthetic hosts and dyes is capable of fluorescence detection of oligonucleotide secondary structures. Multivariate analysis of different fluorescence enhancements—generated using cationic dyes that show affinity for both DNA G-quadruplexes and the synthetic hosts—enables discrimination between G-quadruplex structures of identical length and highly similar topological types. Different G-quadruplexes that display the same folding topology can also be easily differentiated by the number of G-quartets and sequence differences at the 3′ or 5′ ends. The array is capable of both differentiation and classification of the G-quadruplex structures at the same time. This simple non-invasive sensing method does not require the discovery and synthesis of specific G-quadruplex binding ligands, but employs a simple multicomponent approach to ensure wide applicability