Host-guest System Research Articles

Structural insights into 1,4-bis(neopentyloxy)pillar[5]arene and the pyridine host–guest system

The crystal structure of 1,4-bis(neopentyloxy)pillar[5]arene, C95H140N2O10 (TbuP), featuring two encapsulated pyridine molecules, reveals significant host–guest interactions. Interestingly, the pyridine guests are positioned near the neopentyloxy substituents instead of the electron-rich aromatic core of the pillar[5]arene. This spatial arrangement suggests a preference for the pyridine molecules to engage with the aliphatic regions of the host. Detailed analysis of the structural characteristics of this host–guest system (TbuP·2Py), as well as its packing pattern within the crystal network, is presented and discussed.

In Silico Drug Encapsulation Using 2-Hydroxypropyl-β-CD, Tyrosine Kinase and Tyrosinase Inhibition of Dinuclear Cu(II) Carboxylate Complexes

In recent years, copper carboxylate complexes have garnered significant interest for biological applications. This study focuses on 20 Cu(II) carboxylate complexes selected from our previous research. Due to the hydrophobic nature of these complexes, the 2-hydroxypropyl-β-cyclodextrin (2HPβCD) was employed as a carrier to reduce toxicity and increase solubility for controlling drug delivery. Monte Carlo calculations were performed to confirm the interaction between the optimized structures of Cu(II) complexes and 2HPβCD, forming a host-guest system. All the structures were simulated and optimized using DFT-D calculations in Material Studio 2017. The results indicated that a neutral medium is more favorable for the adsorption of these complexes into 2HPβCD. More negative binding energy values suggested strong and energetically favorable adsorption on 2HPβCD. Complexes 4, 5, and 7 exhibited the highest interaction, making them excellent candidates for drug delivery systems. DFT-D calculations were also used to investigate the release of complexes, revealing that complexes 5, 14, and 19 were difficult to release due to their lowest energy. In contrast, complexes 8, 9, and 16 were found to be most efficient to release due to weak non-covalent interactions with 2HPβCD as we can predict from binding energy obtained by DFT-D. No specific trend was observed in the interaction of the complexes with 2HPβCD. Additionally, the effects of these complexes on c-kit tyrosine kinase and Mushroom tyrosinase were studied by molecular docking. The results demonstrated that all the complexes interacted with the active site of respective receptors through hydrophobic interactions. Complexes containing 1,10-phenanthroline and 2,2-bipyrdine were identified as having a strong, spontaneous binding ability with receptors.

Evaluation of All-Atom and Martini 3 Coarse-Grained Force Fields from the Structural Investigation of Nitroxide Spin Probes and Their Confinement in Beta-Cyclodextrin.

Nitroxide radicals have found wide applications as spin labels or probes, and their guest-host interactions with cyclodextrins exhibit enhanced applications in electron spin resonance (ESR) spectroscopy and imaging due to improved biostability toward reducing agents. Although the computational prediction of the guest-host binding has become increasingly common for small ligands, molecular simulations regarding the conformational preferences of hosted spin probes have not been conducted. Here we present molecular dynamics simulations at an atomistic level for a set of four TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) spin probes and thereafter develop coarse-grained models compatible with the recent version of the Martini force field (v 3.0) to tackle their encapsulation in the cavity of β-cyclodextrin (βCD) for which experimental ESR data are available. The results indicate that the atomistic descriptions perform well in relation to the structural parameters derived from X-ray diffraction as well as hydrogen bonding and hydrogen patterns and predict that the guest-host complexation is hydrophobically driven by the presence of a methyl group pair of the spin probe at the cavity center of βCD. The spin probe mobility at the binding site reveals the nitroxide group orientation toward the secondary rim of the cyclodextrin and the alternating presence of the two methyl group pairs inside the cavity, features in agreement with the experimental behavior of the ESR parameters. The coarse-grained parameterizations of TEMPO probes and βCD rely on optimizing the bonded and nonbonded parameters with references to the atomistic simulation results, and they are capable of recovering the orientation and location of the spin probe inside the cyclodextrin cavity predicted by the atomistic guest-host complexes. The results suggest the cyclodextrin host-guest system as a powerful validation suite to evaluate new coarse-grained parameterizations of small ligands and future extensions to functionalized cyclodextrins in inclusion complexes.

Long organic persistent luminescence triggered by photo-induced charge-separation for water-resistant information encryption.

The long persistent luminescence (LPL) phenomenon in the water environment presents us with a broad blueprint to struggle for a new generation of optical materials. However, the realization of water-resistant LPL remains a formidable challenge due to severe quenching of triplet excitons inflowing media. Here, an electron donor-acceptor system is designed based on a B2O3 host and carbon dot (CD) guest, which exhibits deep-blue LPL with a lasting time of about 21 s to the naked eye. The average LPL lifetime is over 2 s, and the LPL quantum yield is 10.78%. This host-guest system possesses charge-separated states and charge-transferred states triggered by an optical source, which is the foundation for LPL. Importantly, in water environments (HCl, NaOH, electrolyte NaCl, and H2O), the LPL of as-obtained CDs@B2O3 can still remain due to high environmental stability of B2O3. Based on the excellent LPL with ultra-long lifetime and water-resistant feature, the CDs@B2O3 successfully applies in water-resistant information encryption.

Encapsulation of an Au25 Nanocluster inside a Porphyrin Nanoring Enhances Singlet Oxygen Generation and Photo-Electrocatalytic CO2 Reduction.

The synthesis of molecular host-guest complexes with enhanced performance, relative to those of their components, is a central theme in supramolecular chemistry. Here we explore a host-guest system consisting of an atomically precise gold nanocluster bound inside a zinc porphyrin nanoring. UV-vis absorption and fluorescence titrations with different sized nanorings revealed strong binding between a pyridinethiol-coated Au25 nanocluster and a nanoring consisting of six zinc porphyrin units, and complexation is confirmed by mass spectrometry. Formation of this assembly enhances the stability of the gold nanocluster. The host-guest complex also exhibits remarkable activity and selectivity for photochemical CO2 to CO conversion and singlet oxygen generation.

Sergeant-and-Soldier Effect in an Organic Room-Temperature Phosphorescent Host-Guest System.

Host-guest systems have emerged as an efficient strategy for promoting organic room temperature phosphorescence (RTP). Despite the advantages of doping guest molecules into a host matrix, the complexity of these systems and the lack of techniques to visualize host-guest interactions at the molecular scale pose significant challenges in understanding the underlying mechanisms. Here, a novel host-guest RTP system is developed by incorporating low concentrations (1-10 mol%) of TPP-4C-BI (guest) into crystalline TPP-4C-Cz (host). Utilizing structural isomerism, the guest molecules are regularly incorporated into the host crystal lattice, resulting in phosphorescence quantum yields almost ten times higher than the pure compounds. The system enabled resolution of the molecular packing of the single crystal through X-ray diffraction, providing unprecedented visualization of host-guest interactions. A "sergeant-and-soldier" effect, where the minority dopant molecules (sergeants) significantly influence the packing arrangement of the host molecules (soldiers), enhances RTP is identified. Further analyses revealed that due to the host molecule's inefficient phosphorescence pathway, its long-lived dark triplets are channeled to the guest via triplet-triplet energy transfer (TTET), allowing the excited energy to radiatively decay more efficiently. These insights advance the understanding of RTP mechanisms and offer practical implications for designing high-efficiency phosphorescent materials.

Modulation of SpyCatcher Ligation Kinetics by SpyTag Thioamide Substitution.

Thioamide substitutions have been shown to impart valuable properties on peptides for biophysical experiments as well as cell or in vivo studies, but a rational understanding of thioamide effects on protein structure and protein-protein interactions is lacking. To elucidate their effects in β-sheet structures, we have used SpyCatcher003-SpyTag003 as a host-guest system to study individual thioamide incorporation at eight different positions in the SpyTag peptide. We have demonstrated that incorporating thioamides into SpyTag at specific positions can result in a ∼2-fold faster ligating complex, as well as >2000-fold slower ligating complex. Biophysical analysis and structural modeling provide a reasonable explanation for most of the thioamide effects, altering hydrogen bond networks as well as modulating an n→π* interaction within the SpyTag peptide. Our findings have important implications for potential applications of thioamide SpyTag variants, where the thioamide could impart protease stability in cells while also controlling the rate of ligation to SpyCatcher. These SpyCatcher-SpyTag host-guest experiments will also help to build a database for predicting thioamide effects on protein structure and function.

Stimulating Chiral Selective Expression of Room Temperature Phosphorescence for Chirality Recognition.

Chiral recognition is crucial for applications in chiral purity assessment and biomedical fields. However, achieving chiral recognition through visible roomtemperature phosphorescence remains challenging. Here, two chiral molecules, designated as host and guest are synthesized, which possess similar structural configurations. A viable strategy involving a chiral configuration-dependent energy transfer process to enable selective phosphorescence expression is proposed, thereby enabling chiral recognition in a host-guest doping system. The chiral and structural similarity between host and guest facilitates efficient Dexter energy transfer due to the reduced spatial distance between the molecules. This mechanism significantly enhances the intensity of red phosphorescence from the guest molecule, characterized by an emission peak at 612nm and a prolonged lifetime of 32.7ms. This work elucidates the mechanism of chiral-dependent energy transfer, demonstrating its potential for selectively expressing phosphorescence in chiral recognition.

Interpenetrated Donor-Acceptor Heterojunctions in 2D Conjugated Dibenzo[g,p]chrysene-Based Kagome Covalent Organic Frameworks.

Dibenzo[g,p]chrysene can be viewed as a constrained propeller-shaped tetraphenylethylene with reduced curvature and has been utilized to construct dual-pore kagome covalent organic frameworks (COFs) with tightly packed two-dimensional (2D) layers owing to its rigid and more planar structural characteristics. Here, we introduce 2D COFs based on the node 4,4',4″,4‴-(dibenzo[g,p]chrysene-2,7,10,15-tetraphenyl)tetraamine (DBCTPTA) featuring extended conjugation compared to the dibenzo[g,p]chrysene-3,6,11,14-tetraamine (DBCTA) node. We establish two exceptionally crystalline imine-linked 2D COFs with a hexagonal dual-pore kagome structure based on the DBCTPTA core. The newly synthesized thienothiophene (TT) and benzodithiophene (BDT)-based DBCTPTA COFs show a tight stacking behavior between adjacent layers. Furthermore, we obtained an unprecedented, interpenetrated electron-donor/acceptor host-guest system with an electron-donating BDT DBCTPTA COF synthesized in situ with the soluble fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) serving as molecular acceptor. The BDT DBCTPTA COF@PCBM film shows a much shorter amplitude-averaged PL lifetime of 7 ± 2 ps compared to 30 ± 4 ps of the BDT DBCTPTA COF film, indicating the light-induced charge transfer process. The successful in situ formation of interpenetrated donor-acceptor heterojunctions within 2D COFs offers a promising strategy for establishing D-A heterojunctions in diverse framework materials with open channel systems.

2,3 : 6,7‐Naphthalene Bis(dicarboximide) Cyclophane: A Photofunctional Host for Ambient Delayed Fluorescence in Solution

AbstractHarvesting triplet excitons of heavy atom‐free purely organic chromophores under aerated conditions is challenging due to the quenching of long‐lived triplet states by molecular oxygen and vibrational dissipation. Herein, we show a supramolecular approach of triplet harvesting via mitigating quenching pathways of a triplet harvester. Specifically, we used a host–guest system based on 2,3 : 6,7‐naphthalene bis(dicarboximide)‐derived cyclophane (NBICy) and carbazole derivative (EtCz). Complexation studies and single‐crystal X‐ray analysis showed the formation of a rigid host–guest complex (K≈104 M−1 in CCl4), resulting in triplet‐exciton stabilization under aerated conditions via mitigating vibrational interference and oxygen quenching. Photophysical studies elucidate the delayed fluorescence emission from the charge‐transfer state (1CT) with a quantum yield (QY) of 6–8 % under ambient conditions which increased up to 36 % in an inert atmosphere.

Fine-Tuning the Microstructure and Photophysical Characteristics of Fluorescent Conjugated Copolymers Using Photoalignment and Liquid-Crystal Ordering.

Replicating the microstructural basis and the near 100% excitation energy transfer efficiency in naturally occurring light-harvesting complexes (LHCs) remains challenging in synthetic energy-harvesting devices. Biological photosynthesis regulates active ensembles of light-absorbing and funneling chlorophylls in proteins in response to fluctuating sunlight. Here, use of long-range liquid crystal (LC) ordering to tailor chain orientation and packing structure in liquid crystalline conjugated polymer (LCCP) layers for bio-mimicry of certain structural basis and light-harvesting properties of LHCs is reported. It is found that long-range orientational ordering in an LC phase of poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) copolymer stabilizes a small fraction of randomly-oriented F8BT nanocrystals dispersed in an amorphous matrix of F8BT chains, resembling a self-doped host-guest system whereby excitation energy funneling and photoluminescence quantum efficiencies are enhanced significantly by triggering 3D donor-to-acceptor Förster resonance energy transfer (FRET) and dominant intrachain emission in the nano-crystal acceptor. Further, photoalignment of nematic F8BT layers is combined with LC orientational ordering to fabricate large-area-extended monodomains exhibiting >60% crystallinity and ≈20nm-long interchain packing order. Remarkably, these monodomains demonstrate strong linearly polarized emission, whilst also promoting a new band-edge absorption species and an extra emissive interchain excited state as compared to the non-aligned films.

Time-Dependent Color-Changing Room-Temperature Phosphorescence Materials with Mutual Achievement between Guest and Host Molecules.

Host-guest doping strategy has gradually become the mainstream in constructing organic room-temperature phosphorescence (RTP) materials. The two-component doped system typically emits monochromatic phosphorescence dominated by the guest molecule, which also means that the intrinsic phosphorescence emission of the host molecule is not well utilized. In this work, a time-dependent color-changing RTP material is constructed based on host-guest doped system, in which the initial yellow phosphorescence stems from the isoquinoline-pyrazole guest and the final cyan phosphorescence originates from the intrinsic emission of the polymer host. The phenomenon of the strong interaction between host and guest molecules leading to their respective intrinsic phosphorescence provides new design inspiration for designing and developing two-component doped materials with RTP properties of color variation over time.

Exploring the Photophysical and Mechanical Behavior of Fluorescent Metal-Organic Framework Monoliths.

Luminescent metal-organic frameworks exhibit great potential as materials for nanophotonic applications because of their programmable properties and tunable structures. In particular, luminescent guests (LG) can be hosted by metal-organic frameworks due to their porosity and guest confinement capacity, forming LG@MOF composite systems. However, such guest-host systems are mainly produced as loose powders, preventing their widespread use in practical devices and technological applications that require implementation of a stable continuum solid. In this regard, using monolithic MOF hosts might be a workable option to solve this challenge. Herein, we reported the facile synthesis and fabrication of novel prototypical sol-gel monolithic systems, designated as LG@monoMOF. Red (rhodamine B), blue (7-methoxycoumarin), and yellow (fluorescein) emitting dyes were encapsulated in a robust UiO-66 monolithic host, resulting in the red, blue, and yellow light-emitting luminescent monoliths. The mechanical and photophysical characterization of the three LG@monoMOF systems was systematically carried out in order to unravel the role of guest-host interactions in the mechanical and optical response of the bespoke LG@monoMOF composites.

Chiroptically Active Host-Guest Composites Using a Terpene-Based Micellar Capsule.

For the design of a new chiroptically active host-guest system, a bent amphiphilic compound was synthesized using cyclic monoterpenes as key biorelated chiral frameworks. In water, the bent amphiphiles form a terpene-based micellar capsule with a core diameter of ∼2 nm in a spontaneous and quantitative fashion. The resultant chiral capsule shows wide-ranging uptake abilities toward achiral fluorescent dyes in water. Notably, relatively strong CD bands are generated from the resultant host-guest composites, e.g., possessing AIE-active tetraphenylethene and sterically demanding BODIPY dyes, through efficient host-to-guest chirality transfer. The composites also display CPL, with moderate to high emission asymmetry factors (|glum| = up to 3.3 × 10-3).

Dual pH and Ca2+-Responsive PEG-Modified Pillar[5]arene-Based Supramolecular Nanodrug Delivery System: Excellent Cargo Encapsulation and Minimal Drug Toxicity.

Chemotherapy is one of the most employed strategies in clinical treatment of cancer. However, reducing medication adverse effects and improving the biological activity remains a significant issue for chemotherapy. We developed a pH and Ca2+-responsive pillar[5]arene-based supramolecular nanodrug delivery system (NDDS) WP5⊃EV@DOX to address the aforementioned challenges. The formation of this NDDS began with the spontaneous formation of supramolecular nanodrug carrier WP5⊃EV in water from PEG-modified pillar[5]arene and the bipyridilium salt derivative EV through simple host-guest interaction. Then the antitumor drug doxorubicin DOX was efficiently loaded with a high encapsulation rate of 84.6 %. Cytotoxicity results indicated that the constructed nanoplatform not only reduced DOX toxicity and side effects on normal cell (293T), but also significantly enhanced the antitumor activity on cancer cell (HepG2). Moreover, in vivo experiments showed that WP5⊃EV@DOX had a longer half-life and higher bioavailability in the blood of mice compared to the nake drug DOX, with increases to 212 % and 179 %, respectively. Therefore, WP5⊃EV@DOX has great potential in tumor therapy and provides a new idea for host-guest drug delivery system.

High-Resolution Cryogenic Spectroscopy of Single Molecules in Nanoprinted Crystals.

We perform laser spectroscopy at liquid helium temperatures (T = 2 K) to investigate single dibenzoterrylene (DBT) molecules doped in anthracene crystals of nanoscopic height fabricated by electrohydrodynamic dripping. Using high-resolution fluorescence excitation spectroscopy, we show that zero-phonon lines of single molecules in printed nanocrystals are nearly as narrow as the Fourier-limited transitions observed for the same guest-host system in the bulk. Moreover, the spectral instabilities are comparable to or less than one line width. By recording super-resolution images of DBT molecules and varying the polarization of the excitation beam, we determine the dimensions of the printed crystals and the orientation of the crystals' axes. Electrohydrodynamic printing of organic nano- and microcrystals is of interest for a series of applications, where controlled positioning of quantum emitters with narrow optical transitions is desirable.

2,3 : 6,7-Naphthalene Bis(dicarboximide) Cyclophane: A Photofunctional Host for Ambient Delayed Fluorescence in Solution.

Harvesting triplet excitons of heavy atom-free purely organic chromophores under aerated conditions is challenging due to the quenching of long-lived triplet states by molecular oxygen and vibrational dissipation. Herein, we show a supramolecular approach of triplet harvesting via mitigating quenching pathways of a triplet harvester. Specifically, we used a host-guest system based on 2,3 : 6,7-naphthalene bis(dicarboximide)-derived cyclophane (NBICy) and carbazole derivative (EtCz). Complexation studies and single-crystal X-ray analysis showed the formation of a rigid host-guest complex (K≈104 M-1 in CCl4), resulting in triplet-exciton stabilization under aerated conditions via mitigating vibrational interference and oxygen quenching. Photophysical studies elucidate the delayed fluorescence emission from the charge-transfer state (1CT) with a quantum yield (QY) of 6-8 % under ambient conditions which increased up to 36 % in an inert atmosphere.

Multifunctional application of planar 2D molecule for light-emitting heterostructures

The object of research is the donor-acceptor compound, organic and hybrid heterostructures based on it. The paper is focused on a comprehensive approach to solving the problem of the efficiency of light-emitting devices, finding new technological and design solutions for the use of organic compounds as multifunctional materials for various types of light-emitting devices. The paper presents the multifunctional application of a planar 2D molecule as an emission layer for typical and inverted types of light-emitting heterostructures, as well as a matrix for a host-guest system using inorganic quantum dots. The developed light-emitting structures are characterized by external quantum efficiency typical for fluorescent devices, but good stability over the entire length of the consumption voltage. QLED brightness is 1600 cd·m-2 and EQE 1.4 %, which are good parameters for use in display technology. Organic LEDs based on planar molecules are promising candidates for use in modern lighting systems. A separate advantage of these light-emitting structures is the multifunctionality of using one compound for different types of light-emitting structures, including inverted heterostructures. Special attention is paid to the technological and design implementation of invert structures, since their geometry allows direct connection to the back board of the n-channel transistor on the substrate. In addition, organic LEDs have low energy consumption and are environmentally friendly due to the absence of toxic substances in their architecture, which creates the prerequisites for saving energy resources and reducing the industrial burden on the environment.

Optimization of the properties of nematic matrix suspended with subtle quantities of the nanoparticles for improved alignment and operating voltage

ABSTRACT The current study examines and reflects the effect of minute quantity of Diamond nanoparticles (DNPs) in the Nematic liquid crystal (NLC) matrix. A well structured and strategized study is performed in order to get a deep understanding about the interactions that might have taken place between the guests and the hosts. Our study professed a significant alteration in the number of parameters of guest-host system in comparison to the pure liquid crystal (LC) matrix that could be found extremely promising for the display devices and low-power switching machines. 0.05, 0.07 and 0.1 wt/wt% concentrations of the NPs incorporated in the LC matrix and the composites are prepared with the high precision weight measurement using electrical balance. Dielectric spectrum is catalogued for both the homogeneous and vertical alignments of sample cells. Threshold voltage and operating voltage are found to be significantly decreased for 0.05 wt/wt% composite. Response time for the prepared composites is profoundly abated which is a crucial factor for the fast response devices. Careful examination of pretilt angles is executed and an improvement in the alignment is found as one more perk of this study.

Mixing Rules for Left-Handed Disordered Metamaterials: Effective-Medium and Dispersion Properties.

Left-handed materials are known to exhibit exotic properties in controlling electromagnetic fields, with direct applications in negative reflection and refraction, conformal optical mapping, and electromagnetic cloaking. While typical left-handed materials are constructed periodic metal-dielectric structures, the same effect can be obtained in composite guest-host systems with no periodicity or structural order. Such systems are typically described by the effective-medium approach, in which the components of the electric permittivity tensor are determined as a function of individual material properties and doping concentration. In this paper, we extend the discussion on the mixing rules to include left-handed composite systems and highlight the exotic properties arising from the effective-medium approach in this framework in terms of effective values and dispersion properties.