Cyclodextrin Host Research Articles

Brighter, More Stable, and Less Toxic: A Host-Guest Interaction-Aided Strategy for Fabricating Fluorescent Silica Nanoparticles and Applying Them in Bioimaging and Biosensing at the Cellular Level.

The exploration of fluorescent tools with distinguished optical properties and favorable biocompatibility is significant for biosensing and bioimaging. We herein present a host-guest interactions aided strategy for fabricating fluorescent silica nanoparticles (FSNPs), which is enabled by cyclodextrin (CD) supermolecules. Compared with conventional FSNPs, the modified products (are named as fluorophore@CD@SNPs) possess several advantages. First, the incorporated fluorophores can thoroughly get rid of their intrinsic aggregation due to CD's inclusion effect, and the fluorescence intensity of the obtained fluorophore@CD@SNPs can enhance 48-67%. The fluorophores can then be well-fixed by the host CD molecules. As a result, the leak rates of the incorporated fluorophores are only 15-17%, which is about 3 times lower than that of conventional ones (42-48%). Notably, the as-prepared fluorophore@CD@SNPs show observable less cytotoxicity as compared with their conventional counterparts, probably due to the substantially decreased leakage of the incorporated fluorophores. Because of prominent properties and versatile fabrication, the proposed fluorophore@CD@SNPs not only possess better performances for cell-imaging but are competent for ratiometric sensing of pH value at living cell using (indicator-reference) integrative silica NPs.

Fast NMR Screening of Macromolecular Complexes by a Paramagnetic Spin Relaxation Filter.

The paramagnetic spin relaxation filter is described for the rapid NMR screening of intermolecular interactions between ligands and macromolecular anionic receptors with large transverse relaxation enhancements (R2p). The addition of micromolar concentrations of Gd3+ to the mixture produces the immediate broadening/suppression of the NMR signals of interacting species while leaving unaffected those of noncompetitive binders (one-dimensional and two-dimensional experiments). The method is highly sensitive, unveiling interactions that are too weak to generate changes in chemical shifts or relaxation times. It is operationally very simple and hence, it is amenable to ready implementation by nonspecialists. Examples of application such as detecting the formation of interpolymer complexes, cyclodextrin host–guest interactions, and the screening of DNA ligands are included that demonstrate the reliability and broad applicability of the method.

A Supramolecular Approach for Liver Radioembolization.

Hepatic radioembolization therapies can suffer from discrepancies between diagnostic planning (scout-scan) and the therapeutic delivery itself, resulting in unwanted side-effects such as pulmonary shunting. We reasoned that a nanotechnology-based pre-targeting strategy could help overcome this shortcoming by directly linking pre-interventional diagnostics to the local delivery of therapy.Methods: The host-guest interaction between adamantane and cyclodextrin was employed in an in vivo pre-targeting set-up. Adamantane (guest)-functionalized macro albumin aggregates (MAA-Ad; d = 18 μm) and (radiolabeled) Cy5 and β-cyclodextrin (host)-containing PIBMA polymers (99mTc-Cy50.5CD10PIBMA39; MW ~ 18.8 kDa) functioned as the reactive pair. Following liver or lung embolization with (99mTc)-MAA-Ad or (99mTc)-MAA (control), the utility of the pre-targeting concept was evaluated after intravenous administration of 99mTc-Cy50.5CD10PIBMA39.Results: Interactions between MAA-Ad and Cy50.5CD10PIBMA39 could be monitored in solution using confocal microscopy and were quantified by radioisotope-based binding experiments. In vivo the accumulation of the MAA-Ad particles in the liver or lungs yielded an approximate ten-fold increase in accumulation of 99mTc-Cy50.5CD10PIBMA39 in these organs (16.2 %ID/g and 10.5 %ID/g, respectively) compared to the control. Pre-targeting with MAA alone was shown to be only half as efficient. Uniquely, for the first time, this data demonstrates that the formation of supramolecular interactions between cyclodextrin and adamantane can be used to drive complex formation in the chemically challenging in vivo environment.Conclusion: The in vivo distribution pattern of the cyclodextrin host could be guided by the pre-administration of the adamantane guest, thereby creating a direct link between the scout-scan (MAA-Ad) and delivery of therapy.

NIR-induced spatiotemporally controlled gene silencing by upconversion nanoparticle-based siRNA nanocarrier

Spatiotemporal control over the release or activation of biomacromolecules such as siRNA remains a significant challenge. Light-controlled release has gained popularity in recent years; however, a major limitation is that most photoactivable compounds/systems respond only to UV irradiation, but not near-infrared (NIR) light that offers a deeper tissue penetration depth and better biocompatibility. This paper reports a simple NIR-to-UV upconversion nanoparticle (UCNP)-based siRNA nanocarrier for NIR-controlled gene silencing. siRNA is complexed onto a NaYF4:Yb/Tm/Er UCNP through an azobenzene (Azo)–cyclodextrin (CD) host–guest interaction. The UV emission generated by the NIR-activated UCNP effectively triggers the trans-to-cis photoisomerization of azobenzene, thus leading to the release of siRNA due to unmatched host−guest pairs. The UCNP-siRNA complexes are also functionalized with PEG (i.e., UCNP-(CD/Azo)-siRNA/PEG NPs), targeting ligands (i.e., EGFR-specific GE11 peptide), acid-activatable cell-penetrating peptides (i.e., TH peptide), and imaging probes (i.e., Cy5 fluorophore). The UCNP-(CD/Azo)-siRNA/PEG NPs with both GE11 and TH peptides display a high level of cellular uptake and an excellent endosomal/lysosomal escape capability. More importantly, NIR-controlled spatiotemporal knockdown of GFP expression is successfully achieved in both a 2D monolayer cell model and a 3D multicellular tumor spheroid model. Thus, this simple and versatile nanoplatform has great potential for the selective activation or release of various biomacromolecules.

Reorganizing Polymer Chains with Cyclodextrins.

During the past several years, we have been utilizing cyclodextrins (CDs) to nanostructure polymers into bulk samples whose chain organizations, properties, and behaviors are quite distinct from neat bulk samples obtained from their solutions and melts. We first form non-covalently bonded inclusion complexes (ICs) between CD hosts and guest polymers, where the guest chains are highly extended and separately occupy the narrow channels (~0.5–1.0 nm in diameter) formed by the columnar arrangement of CDs in the IC crystals. Careful removal of the host crystalline CD lattice from the polymer-CD-IC crystals leads to coalescence of the guest polymer chains into bulk samples, which we have repeatedly observed to behave distinctly from those produced from their solutions or melts. While amorphous polymers coalesced from their CD-ICs evidence significantly higher glass-transition temperatures, Tgs, polymers that crystallize generally show higher melting and crystallization temperatures (Tms, Tcs), and some-times different crystalline polymorphs, when they are coalesced from their CD-ICs. Formation of CD-ICs containing two or more guest homopolymers or with block copolymers can result in coalesced samples which exhibit intimate mixing between their common homopolymer chains or between the blocks of the copolymer. On a more practically relevant level, the distinct organizations and behaviors observed for polymer samples coalesced from their CD-ICs are found to be stable to extended annealing at temperatures above their Tgs and Tms. We believe this is a consequence of the structural organization of the crystalline polymer-CD-ICs, where the guest polymer chains included in host-IC crystals are separated and confined to occupy the narrow channels formed by the host CDs during IC crystallization. Substantial degrees of the extended and un-entangled natures of the IC-included chains are apparently retained upon coalescence, and are resistant to high temperature annealing. Following the careful removal of the host CD lattice from each randomly oriented IC crystal, the guest polymer chains now occupying a much-reduced volume may be somewhat “nematically” oriented, resulting in a collection of randomly oriented “nematic” regions of largely extended and un-entangled coalesced guest chains. The suggested randomly oriented nematic domain organization of guest polymers might explain why even at high temperatures their transformation to randomly-coiling, interpenetrated, and entangled melts might be difficult. In addition, the behaviors and uses of polymers coalesced from their CD-ICs are briefly described and summarized here, and we attempted to draw conclusions from and relationships between their behaviors and the unique chain organizations and conformations achieved upon coalescence.

Dual-stimuli responsive nanoparticles (UCNP-CD@APP) assembled by host-guest interaction for drug delivery

In this paper, dual-sensitive nanoparticles with pH- and photo- responsibility were prepared through host-guest interaction. Self-synthesized copolymer azobenzene -poly-2-(diisopropylamino) ethyl methacrylate – methoxypolyethylene glycols (AZO-PDPAn-PEG45, APP) acted as a guest and inserted into the host cyclodextrins (β-CD) automatically, which had been grafted onto the surface of upconversion nanoparticle (UCNP-CD). The insertion of APP was reversibly due to the alternating cis-trans isomerism of AZO under UV and Vis light, which produced simultaneously by UCNP when irradiated by near-infrared (NIR, 980nm). And, the PDPA block provided a pH sensitive “lock” for releasing cargos. The self-assembled UCNP-CD@APPs were tried to incorporate anti-cancer drug DOX and were proved to release DOX controllably under stimulus of pH and NIR. During the whole process, the reversible isomerism behavior of AZO acted as a ‘perpetual stirrer’ resulting in a quick release. The UCNP-CD@APP nanoparticles displayed good biocompatibility via MTT assay. Meanwhile, the DOX loaded in UCNP-CD@APP exhibited an obvious cytotoxic effect on HeLa cells than free DOX.

Evaluating Force Field Performance in Thermodynamic Calculations of Cyclodextrin Host–Guest Binding: Water Models, Partial Charges, and Host Force Field Parameters

Computational prediction of noncovalent binding free energies with methods based on molecular mechanical force fields has become increasingly routine in drug discovery projects, where they promise to speed the discovery of small molecule ligands to bind targeted proteins with high affinity. Because the reliability of free energy methods still has significant room for improvement, new force fields, or modifications of existing ones, are regularly introduced with the aim of improving the accuracy of molecular simulations. However, comparatively little work has been done to systematically assess how well force fields perform, particularly in relation to the calculation of binding affinities. Hardware advances have made these calculations feasible, but comprehensive force field assessments for protein–ligand sized systems still remain costly. Here, we turn to cyclodextrin host–guest systems, which feature many hallmarks of protein–ligand binding interactions but are generally much more tractable due to their small size. We present absolute binding free energy and enthalpy calculations, using the attach-pull-release (APR) approach, on a set of 43 cyclodextrin-guest pairs for which experimental ITC data are available. The test set comprises both α- and β-cyclodextrin hosts binding a series of small organic guests, each with one of three functional groups: ammonium, alcohol, or carboxylate. Four water models are considered (TIP3P, TIP4Pew, SPC/E, and OPC), along with two partial charge assignment procedures (RESP and AM1-BCC) and two cyclodextrin host force fields. The results suggest a complex set of considerations when choosing a force field for biomolecular simulations. For example, some force field combinations clearly outperform others at the binding enthalpy calculations but not for the binding free energy. Additionally, a force field combination which we expected to be the worst performer gave the most accurate binding free energies – but the least accurate binding enthalpies. The results have implications for the development of improved force fields, and we propose this test set, and potential future elaborations of it, as a powerful validation suite to evaluate new force fields and help guide future force field development.

Theranostic Prodrug Vesicles for Imaging Guided Codelivery of Camptothecin and siRNA in Synergetic Cancer Therapy.

The construction of prodrugs has been a popular strategy to overcome the limitations of chemotherapeutic drugs. However, complicated synthesis procedures and laborious purification steps make the fabrication of amphiphilic prodrugs rather difficult. By harnessing the concept of host-guest interaction, we designed and prepared a supra-amphiphile consisting of a dendritic cyclodextrin host and an adamantane/naphthalimide-modified camptothecin guest through glutathione-responsive disulfide linkage. This host-guest complex could self-assemble in aqueous solution to give nanosized vesicles. When the disulfide bond in adamantane/naphthalimide-modified camptothecin was cleaved by glutathione, the fluorescence of the freed adamantane/naphthalimide unit showed a significant red shift with enhanced intensity. Such glutathione-responsive fluorescence change allows for intracellular imaging and simultaneous monitoring of drug release in real time. On account of abundant positively charged amine groups on the supramolecular vesicle surface, siRNA (siPlK1) could be efficiently loaded on the vesicle. The gel retardation and fluorescence experiments proved that the siPlK1 was successfully bonded to the supramolecular vesicle. The vesicle with dendritic cyclodextrin ring exhibited negligible cytotoxicity even at high concentrations, avoiding the shortcoming of cytotoxicity from commonly used gene vectors. In vitro studies demonstrated that the loaded siRNA was transported into cancer cells to improve cancer therapeutic efficacy. Thus, we developed a prodrug-based supramolecular amphiphile via the host-guest interaction with better therapeutic performance than free camptothecin. The assembled system was utilized as a drug/gene vector to achieve combinational gene therapy and chemotherapy with a synergistic effect, providing an alternative strategy to deliver both prodrug and therapeutic gene.

Designed positively charged cyclodextrin hosts with enhanced binding of penicillins as carriers for the delivery of antibiotics: The case of oxacillin

In an effort to identify the optimal cyclodextrin (CD) host for delivery of penicillins to mammalian cells that will also offer protection against β-lactamase-induced hydrolysis, nuclear magnetic resonance (NMR) spectroscopy and isothermal titration calorimetry (ITC) have been employed to study the inclusion complexes formed in aqueous solution between designed CD derivatives and two aminopenicillins, ampicillin and amoxicillin, and two antistaphylococcal penicillins, methicillin and oxacillin. Anionic and cationic thioether-substituted-β- and −γCD derivatives were thus synthesized and compared with the neutral, parent CDs for complexation with the penicillins. The synthesized derivatives were shown to present ∼20% elongated cavity space in solution. Moreover, the cationic ones are >98% protonated at physiological pH. The most efficient host was the positively charged octakis[6-(2-aminoethylthio)-6-deoxy]-γ-CD (γCys) that formed the strongest complex with oxacillin (Kb ∼1700M−1) in an enthalpically and entropically favorable process (ΔHb=−10.5kJ/mol,TΔSb=8.0kJ/mol). In vitro biological tests demonstrated that γCys reduces 2.3-fold the rate of hydrolysis of oxacillin in the presence of oxa-1 β-lactamase while displaying cell crossing capability and efficient internalization into macrophages as well as a sufficiently safe cytotoxicity profile. Overall, γCys could be considered as a promising vehicle for protection and delivery of oxacillin.

Encapsulation of lemongrass oil with cyclodextrins by spray drying and its controlled release characteristics.

Inclusion of the two isomers of citral (E-citral and Z-citral), components of lemongrass oil, was investigated within the confines of various cyclodextrin (α-CD, β-CD and γ-CD) host molecules. Aqueous complex formation constants for E-citral with α-CD, β-CD and γ-CD were determined to be 123, 185, and 204 L/mol, respectively, whereas Z-citral exhibited stronger affinities (157, 206, and 253 L/mol, respectively). The binding trend γ-CD>β-CD>α-CD is a reflection of the more favorable geometrical accommodation of the citral isomers with increasing cavity size. Encapsulation of lemongrass oil within CDs was undertaken through shaking citral:CD (1:1, 1.5:1, and 2:1 molar ratio) mixtures followed by spray drying. Maximum citral retention occurred at a 1:1 molar ratio with β-CD and α-CD demonstrating the highest levels of total E-citral and Z-citral retention, respectively. Furthermore, the β-CD complex demonstrated the slowest release rate of all inclusion complex powders.

Factors Affecting the Formation of 2:1 Host:Guest Inclusion Complexes of 2-[(R-Phenyl)amine]-1,4-naphthalenediones (PAN) in β- and γ-Cyclodextrins.

The molecular hosts cyclodextrins form inclusion complexes with a wide variety of guests, resulting in complexes with various host:guest stoichiometries. In the case of a series of 19 1,4-naphthoquinolines as guests with either β- or γ-cyclodextrin studied using electrospray mass spectroscopy, in most cases only 1:1 complexes were observed, with 2:1 host:guest complexes observed in just 6 out of 38 host:guest combinations. It is shown that these higher-order complexes were observed only in the case of small (or no) electronically withdrawing substituents, and were much less likely in the case of the larger γ-cyclodextrin host. The size and electronic properties of the substituents involved shows that both steric and electronic factors must be taken into account in predicting which cyclodextrin host:guest stoichiometries will be stable enough to form (or once formed, be robust enough to be observed in the ESI-MS experiments). It is clear that the prediction of host-guest stoichiometry for a specific host-guest pair is complicated, and involves a subtle interplay of both electronic and steric factors. However, there are definite trends, which can be used to help predict host:guest stoichiometry for a given host-guest pair.

Multicolor Photoluminescence Including White-Light Emission by a Single Host-Guest Complex.

Achieving multicolor photoluminescence, especially white-light emission, under mild conditions based on a single fluorescent compound is a great challenge. Herein, we report a novel colorful-emission host-guest complex BPCY, which is composed of a two-arm fluorescent guest molecule (BPC) and γ-cyclodextrin (γ-CD) as the host molecule. BPC bears a unique asymmetrical donor-acceptor-donor (D1-A+∼D2)-type structure, where D1, A+, and D2 stand for the binaphthol electron donor, pyridinium electron acceptor, and coumarin electron donor, respectively. The luminescence property of BPC shows dual-sensitivity, i.e., toward the excitation wavelength and the cyclodextrin host molecule. Under certain conditions, the complex shows three different emission wavelengths, allowing the realization of multicolor photoluminescence, including red (R), green (G), and blue (B) as well as various intermediate colors by orthogonally modulating these two stimuli. In this way, nearly pure white-light emission with CIE coordinates (0.33, 0.34) could be generated. A combination of structural, spectroscopic, and computational simulation studies revealed the occurrence of synergetic mechanistic processes for the stimuli-responsive multicolor luminescence of the BPCY complex, namely, host-enhanced intramolecular charge-transfer (ICT) and host-induced restriction of intramolecular rotation (RIR). This new supramolecular complex with superior multicolor emission abilities may find wide applications in the fields of information processing and display media. Furthermore, the molecular design rationale presented here may provide a new design strategy for the development of high performance optical materials using a single supramolecular platform.

Evaluation of Generalized Born Models for Large Scale Affinity Prediction of Cyclodextrin Host-Guest Complexes.

Binding affinity prediction with implicit solvent models remains a challenge in virtual screening for drug discovery. In order to assess the predictive power of implicit solvent models in docking techniques with Amber scoring, three generalized Born models (GBHCT, GBOBCI, and GBOBCII) available in Dock 6.7 were utilized, for determining the binding affinity of a large set of β-cyclodextrin complexes with 75 neutral guest molecules. The results were compared to potential of mean force (PMF) free energy calculations with four GB models (GBStill, GBHCT, GBOBCI, and GBOBCII) and to experimental data. Docking results yield similar accuracy to the computationally demanding PMF method with umbrella sampling. Neither docking nor PMF calculations reproduce the experimental binding affinities, however, as indicated by a small Spearman rank order coefficient (∼0.5). The binding energies obtained from GB models were decomposed further into individual contributions of the binding partners and solvent environments and compared to explicit solvent simulations for five complexes allowing for rationalizing the difference between explicit and implicit solvent models. An important observation is that the explicit solvent screens the interaction between host and guest much stronger than GB models. In contrast, the screening in GB models is too strong in solutes, leading to overestimation of short-range interactions and too strong binding. It is difficult to envision a way of overcoming these two opposite effects.

Inclusion of an Anthracene-based Fluorophore within Molecular Containers: A Comparative Study of the Cucurbituril and Cyclodextrin Host Families.

In this paper, the binding interaction of a promising chloride channel blocker, 9-methyl anthroate (9-MA), with two different classes of molecular containers, β-cyclodextrins (β-CD and methyl-β-CD) and cucurbit[7]uril, having comparable cavity dimensions, has been thoroughly demonstrated via inspection of the modulation of the excited-state properties of the emissive molecule. Spectral data suggest that CB7 encapsulates the probe more efficiently in a 1:2 fashion, whereas the efficacies of β-CDs are relatively less and the corresponding stoichiometry is 1:1. Interestingly, despite being thermodynamically much more favorable than the probe-β-CD complexation equilibria, the fraction of probe-CB7 complex formed is appreciably smaller with respect to that of probe-β-CD complexes. This apparent inconsistency has been addressed via the proposition that since the formation of a 1:2 complex is entropically disadvantageous, it is anticipated that the activation barrier of the corresponding reaction is reasonably high, and thus only a small fraction of the reactants are able to surpass the energy barrier to form the products. This proposition has been thoroughly corroborated by fluorescence lifetime measurements at different temperatures.

A hybrid hydrogel based on clay nanoplatelets and host–guest inclusion complexes

Abstract In this work, a monomer with double bond was introduced to the surface of clay nanosheets via inclusion complexation between cyclodextrin (CD) host and azobenzene (Azo) guest, as well as electrostatic interaction between clay nanoplatelets and cations of azobenzene derivatives. The obtained supra-structure acts as a supramolecular cross-linker in its copolymerization with macromonomer PEG resulting in a hybrid supramolecular hydrogel. Only viscous liquid was obtained in the absence of clay nanoplatelets, revealing the supramolecular cross-linker played an important role in the hydrogel formation. Such hybrid supramolecular hydrogel exhibited good stability and shear thinning property.

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host-guest complexation.

The employment of cyclodextrin host–guest complexation to construct supramolecular assemblies with an emphasis on polymer networks is reviewed. The main driving force for this supramolecular assembly is host–guest complexation between cyclodextrin hosts and guest groups either of which may be discrete molecular species or substituents on a polymer backbone. The effects of such complexation on properties at the molecular and macroscopic levels are discussed. It is shown that cyclodextrin complexation may be used to design functional polymer materials with tailorable properties, especially for photo-, pH-, thermo- and redox-responsiveness and self-healing.

A Hybrid Supramolecular Polymeric Hydrogel with Rapid Self-Healing Property.

A hybrid supramolecular polymeric hydrogel is conveniently constructed via host-guest interaction of a host cyclodextrin polymer (poly-CD) with a guest α-bromonaphthalene polymer (poly-BrNp) and mixing with 6-thio-β-cyclodextrin (β-SH-CD) modified gold nanoparticles (GPCDs) in aqueous solution. According to the dynamic oscillatory data, the hydrogel exhibits markedly enhanced stiffness compared with the GPCD-free one (both G' and G" values are almost twice as high as those of the original GPCD-free hydrogel) due to the introduction of the inorganic gold nanoparticles. This hybrid supramolecular polymeric hydrogel has a rapid and excellent self-healing property (only about 1 min, and the G' and G" of the self-healed hydrogel almost turned back to their original levels after 1 hour) in air (without adding any solvent or additive).

Inclusion excluded: Chiroptical sensing of the external surface of sulfated cyclodextrins

It is shown that the heparin antagonist bis-aminoquinoline derivative surfen interacts with sulfated cyclodextrins in a unique fashion. Analysis of the UV spectroscopic data revealed exceptionally strong association (Ka ∼ 107 M−1) of several surfen molecules to the external surface of the cyclodextrin hosts. H-bonded to the sulfate groups in 1:1 stoichiometry, the drug molecules form a chiral layer around the macrocycles. Due to the steric proximity, dipole–dipole coupling occurs between the adjacent aminoquinoline rings that accounts for the large UV hypochromism and the induced exciton couplet in the circular dichroism spectra.

Photophysical and quantum chemical studies on the interactions of oxazine-1 dye with cucurbituril macrocycles.

Supramolecular host-guest interaction of cationic oxazine-1 (OX1) dye with two cucurbit[n]uril (CBn) hosts, namely, CB7 and CB8, has been investigated using photophysical and quantum chemical studies. Both CB7 and CB8 display much stronger binding affinities for OX1 dye compared to conventional cyclodextrin (CD) hosts, which arises due to strong ion-dipole interaction in stabilizing the dye-host inclusion complexes in the present systems. From photophysical studies supported by (1)H NMR results and quantum chemical calculations, it is inferred that 1:1 inclusion complexes are mainly formed in the present systems, though a small percentage of 1:2 (dye·host2) complexes are also indicated from time-resolved (TR) fluorescence studies. Longer rotational relaxation times for dye-CBn systems compared to the free dye as estimated from TR anisotropy studies support the inclusion complex formation in the present systems. The binding constant value is estimated to be significantly higher for the OX1-CB7 system than the OX1-CB8 system, and these results are in accordance with compatible portal diameter of CB7 cavity compared to the much larger portal diameter of CB8 cavity relative to the width of the OX1 molecule. Accordingly, CB7 cavity renders a relatively stronger binding than the CB8 cavity for an axially incorporated OX1 dye into the host cavity. Results from the quantum chemical calculations are overall supportive to the inferences drawn from photophysical measurements. Observed results clearly suggest that the dimensions of the CBn cavities play an important role in determining the interaction strength and stoichiometry of the host-guest complexes formed and thus bring out significant changes in the photophysical properties of the bound dye. The host-assisted modulation in the photophysical properties of the dye, as observed in the present study, has a direct relevance to applications like aqueous dye lasers, sensors, fluorescence assays, and so on.

Facile synthesis of oligoyne amphiphiles and their rotaxanes.

Carbon-rich organic compounds containing a series of conjugated triple bonds (oligoynes) are relevant synthetic targets, but an improved access to oligoynes bearing functional groups would be desirable. Here, we report the straightforward synthesis of two series of oligoyne amphiphiles with glycoside or carboxylate polar head groups, investigate their self-assembly behavior in aqueous media, and their use as precursors for the formation of oligoyne rotaxanes with cyclodextrin hosts. To this end, we employed mono-, di-, or triacetylenic building blocks that gave access to the corresponding zinc acetylides in situ and allowed for the efficient elongation of the oligoyne segment in few synthetic steps via a Negishi coupling protocol. Moreover, we show that the obtained oligoyne derivatives can be deprotected to yield the corresponding amphiphiles. Depending on their head groups, the supramolecular self-assembly of these amphiphiles gave rise to different types of carbon-rich colloidal aggregates in aqueous media. Furthermore, their amphiphilicity was exploited for the preparation of novel oligoyne cyclodextrin rotaxanes using simple host-guest chemistry in water.