Supramolecular Switch Research Articles

Reversible Multi-Color optical switch utilizing tetraphenylethylene and spiropyran Complexes: Applications in advanced information encryption

In this paper, we introduced a strategic methodology to obtain time-resolved encryption utilizing a new technique. This method utilizes a reversible supramolecular optical switch, which is based on complexes consisting of tetraphenylethylene and spiropyran. Notably, these components are separately attached at the focal point of the same cholesterol-based unit, wherein the cholesterol-based unit can provide the essential driving forces to form complexes. A series of complexes were prepared with varying molar ratios (TPE/SP), allowing for the tuning of fluorescence emission. The supramolecular system leverages hydrogen bonding, van der Waals forces, and other non-covalent interactions to orchestrate the collaboration between the fluorophores (tetraphenylethylene) and the photochromic molecule (spiropyran). This coordination results in exceptional photochromic attributes, including rapid response, high contrast, and the capability to regulate fluorescence. The system is capable of achieving tunable dynamic fluorescence emission that transitions from brilliant blue to light purple and finally to red through fluorescence resonance energy transfer (FRET) after successive irradiation periods. Additionally, by fine-tuning the ratio of tetraphenylethylene to spiropyran, different dynamic fluorescence emission can be precisely manipulated. It is rarely reported that complexes accomplish time-dependent fluorescence emission with high-contrast. We are confident that the complexes, grounded on cholesterol unit, hold promise for broader applicability in developing innovative time-dependent fluorescent materials. Such materials can be effectively utilized for time-dependent information encryption, thereby bolstering security measures against unauthorized access.

Oligo-Adenine Derived Secondary Nucleic Acid Frameworks: From Structural Characteristics to Applications.

Oligo-adenine (polyA) is primarily known for its critical role in mRNA stability, translational status, and gene regulation. Beyond its biological functions, extensive research has unveiled the diverse applications of polyA. In response to environmental stimuli, single polyA strands undergo distinctive structural transitions into diverse secondary configurations, which are reversible upon the introduction of appropriate counter-triggers. In this review, we systematically summarize recent advances of noncanonical structures derived from polyA, including A-motif duplex, A-cyanuric acid triplex, A-coralyne-A duplex, and T ⋅ A-T triplex. The structural characteristics and mechanisms underlying these conformations under specific external stimuli are addressed, followed by examples of their applications in stimuli-responsive DNA hydrogels, supramolecular fibre assembly, molecular electronics and switches, biosensing and bioengineering, payloads encapsulation and release, and others. A detailed comparison of these polyA-derived noncanonical structures is provided, highlighting their distinctive features. Furthermore, by integrating their stimuli-responsiveness and conformational characteristics, advanced material development, such as pH-cascaded DNA hydrogels and supramolecular fibres exhibiting dynamic structural transitions adapting environmental cues, are introduced. An outlook for future developments is also discussed. These polyA derived, stimuli-responsive, noncanonical structures enrich the arsenal of DNA "toolbox", offering dynamic DNA frameworks for diverse future applications.

A Foldaxane-Based Supramolecular Muscle-Like Switch.

[cn]daisy chain molecular muscle architectures are self-assemblies of hermaphrodite monomers, which usually contain a macrocycle unit linked to a molecular thread that contains sites of interactions - i. e. molecular stations - for the macrocycle. In these multiply threaded structures, altering with control the affinity between macrocycles and stations allows for contraction and extension of the molecule, which is reminiscent of the operation of a muscle. Besides, the field that consists of combining helix and template-containing rods to design foldaxane supramolecular assemblies is still underexplored. By using foldamer units as surrogates for macrocycles, Gan et al. reported the first supramolecular muscle-like foldamer-containing switch that can adopt, after chemical stimulus, either a contracted co-conformational state or a degenerate-like state for which a slow exchange occurred between the contracted and the stretched state.

Mesoporous silica nanoparticles as a drug delivery mechanism.

Research in intelligent drug delivery systems within the field of biomedicine promises to enhance drug efficacy at disease sites and reduce associated side effects. Mesoporous silica nanoparticles (MSNs), characterized by their large specific surface area, appropriate pore size, and excellent biocompatibility, have garnered significant attention as one of the most effective carriers for drug delivery. The hydroxyl groups on their surface are active functional groups, facilitating easy functionalization. The installation of controllable molecular machines on the surface of mesoporous silica to construct nanovalves represents a crucial advancement in developing intelligent drug delivery systems (DDSs) and addressing the issue of premature drug release. In this review, we compile several notable and illustrative examples of MSNs and discuss their varied applications in DDSs. These applications span regulated and progressive drug release mechanisms. MSNs hold the potential to enhance drug solubility, improve drug stability, and mitigate drug toxicity, attributable to their ease of functionalization. Furthermore, intelligent hybrid nanomaterials are being developed, featuring programmable properties that react to a broad spectrum of stimuli, including light, pH, enzymes, and redox triggers, through the use of molecular and supramolecular switches.

Supramolecular Switch for the Regulation of Antibacterial Efficacy of Near-Infrared Photosensitizer.

The global antibiotic resistance crisis has drawn attention to the development of treatment methods less prone to inducing drug resistance, such as antimicrobial photodynamic therapy (aPDT). However, there is an increasing demand for new photosensitizers capable of efficiently absorbing in the near-infrared (NIR) region, enabling antibacterial treatment in deeper sites. Additionally, advanced strategies need to be developed to avert drug resistance stemming from prolonged exposure. Herein, we have designed a conjugated oligoelectrolyte, namely TTQAd, with a donor-acceptor-donor (D-A-D) backbone, enabling the generation of reactive oxygen species (ROS) under NIR light irradiation, and cationic adamantaneammonium groups on the side chains, enabling the host-guest interaction with curcubit[7]uril (CB7). Due to the amphiphilic nature of TTQAd, it could spontaneously form nanoassemblies in aqueous solution. Upon CB7 treatment, the positive charge of the cationic adamantaneammonium group was largely shielded by CB7, leading to a further aggregation of the nanoassemblies and a reduced antibacterial efficacy of TTQAd. Subsequent treatment with competitor guests enables the release of TTQAd and restores its antibacterial effect. The reversible supramolecular switch for regulating the antibacterial effect offers the potential for the controlled release of active photosensitizers, thereby showing promise in preventing the emergence of drug-resistant bacteria.

Photocontrolled Reversibly Chiral-Ordered Assembly Based on Cucurbituril.

Chirality transfer and regulation, accompanied by morphology transformation, arouse widespread interest for application in materials and biological science. Here, a photocontrolled supramolecular chiral switch is fabricated from chiral diphenylalanine (l-Phe-l-Phe, FF) modified with naphthalene (2), achiral dithienylethene (DTE) photoswitch (1), and cucurbit[8]uril (CB[8]). Chirality transfer from the chiral FF moiety of 2 to a charge-transfer (CT) heterodimer consisting of achiral guest 1 and achiral naphthalene (NP) in 2 has been unprecedented achieved via the encapsulation of CB[8]. On the contrary, chirality transfer from chiral FF to NP cannot be conducted in only guest 2. Crucially, induced circular dichroism of the heterodimer can be further modulated by distinct light, attributing to reversible photoisomerization of the DTE. Meanwhile, topological nanostructures are changed from one-dimensional (1D) nanofibers to two-dimensional (2D) nanosheets in the orderly assembling process of the heterodimer, which further achieved reversible interconversion between 2D nanosheets and 1D nanorods with tunable-induced chirality stimulated by diverse light.

Programmable supramolecular chirality in non-equilibrium systems affording a multistate chiroptical switch

The dynamic regulation of supramolecular chirality in non-equilibrium systems can provide valuable insights into molecular self-assembly in living systems. Herein, we demonstrate the use of chemical fuels for regulating self-assembly pathway, which thereby controls the supramolecular chirality of assembly in non-equilibrium systems. Depending on the nature of different fuel acids, the system shows pathway-dependent non-equilibrium self-assembly, resulting in either dynamic self-assembly with transient supramolecular chirality or kinetically trapped self-assembly with inverse supramolecular chirality. More importantly, successive conducting of chemical-fueled process and thermal annealing process allows for the sequential programmability of the supramolecular chirality between four different chiral hydrogels, affording a new example of a multistate supramolecular chiroptical switch that can be recycled multiple times. The current finding sheds new light on the design of future supramolecular chiral materials, offering access to alternative self-assembly pathways and kinetically controlled non-equilibrium states.

A pillar[5]arene noncovalent assembly boosts a full-color lanthanide supramolecular light switch.

A photo-responsive full-color lanthanide supramolecular switch was constructed from a synthetic 2,6-pyridine dicarboxylic acid (DPA)-modified pillar[5]arene (H) complexing with lanthanide ion (Ln3+ = Tb3+ and Eu3+) and dicationic diarylethene derivative (G1) through a noncovalent supramolecular assembly. Benefiting from the strong complexation between DPA and Ln3+ with a 3 : 1 stoichiometric ratio, the supramolecular complex H/Ln3+ presented an emerging lanthanide emission in the aqueous and organic phase. Subsequently, a network supramolecular polymer was formed by H/Ln3+ further encapsulating dicationic G1via the hydrophobic cavity of pillar[5]arene, which greatly contributed to the increased emission intensity and lifetime, and also resulted in the formation of a lanthanide supramolecular light switch. Moreover, full-color luminescence, especially white light emission, was achieved in aqueous (CIE: 0.31, 0.32) and dichloromethane (CIE: 0.31, 0.33) solutions by the adjustment of different ratios of Tb3+ and Eu3+. Notably, the photo-reversible luminescence properties of the assembly were tuned via alternant UV/vis light irradiation due to the conformation-dependent photochromic energy transfer between the lanthanide and the open/closed-ring of diarylethene. Ultimately, the prepared lanthanide supramolecular switch was successfully applied to anti-counterfeiting through the use of intelligent multicolored writing inks, and presents new opportunities for the design of advanced stimuli-responsive on-demand color tuning with lanthanide luminescent materials.

Host-guest interaction enabled chiroptical property, morphology transition, and phase switch in azobenzene-glutamide amphiphile based hydrogel

To achieve the regulation of both chirality and nanostructure in supramolecular gel is significant and challenging. Here, we prepare a supramolecular hydrogel system by an low-molecule-weight-gelator C4AzoGlu in aqueous solution. C4AzoGlu hydrogel show supramolecular chirality and a structure of nanotwists. When C4AzoGlu complex with α-Cyclodextrin in water, the supramolecular chirality switch, the morphology transition from nanotwists to precipitate and the phase switch from gel to sol could be realized by photoirradiation, which is caused by the trans-cis isomerization of the azobenzene group. This work may provide some insights to the chiroptical property and morphology transition based on host-guest gel formed in aqueous solution.

Supramolecular Radical Switches Regulated by Host‐Guest Chemistry

Comprehensive SummaryWater‐soluble thermal initiators are important radical sources to be applied in various fields. However, the uncontrolled radical generation from the high sensitivity of initiators may cause disadvantages in the applications. Here, we present a series of supramolecular radical switches regulated by the host‐guest chemistry between initiators and cucurbit[8]uril (CB [8]). Thermal initiators (VA‐044, VA‐056, VA‐057) can be spontaneously encapsulated into the cavity of CB [8] to “turn off” their radical‐generation ability. Their activity will instantaneously “turn on” in the presence of other competitors such as 1‐adamantylamine (ADA). Further, we demonstrated the free radical polymerization of N‐isopropylacrylamide using initiators, inhibiting its activity by binding with CB [8] and initiating reaction by adding ADA. These novel supramolecular radical switches provide a facile strategy to control the generation of free radicals in a “plug‐and‐play” manner, which may arouse research interests in polymerization, catalysis, and the biomedical field.

Cucurbit[8]uril Confined 6‐Bromoisoquinoline Derivative Dicationic Phosphorescent Energy Transfer Supramolecular Switch for Lysosome Targeted Imaging

AbstractPhosphorescent materials constructed by macrocyclic host confined guest has become a research hotspot in bioimaging. Herein, a highly efficient phosphorescent light‐harvesting supramolecular switch constructed by cucurbit[8]uril (CB[8]) encapsulated dicationic 6‐bromoisoquinoline derivative (G), sulfonatocalix[4]arene (SC4AD), near‐infrared (NIR) fluorescence dyes, and diarylethene molecular switch (1) is reported. First, the resulting supramolecular foldamer formed by G and CB[8] works as a phosphorescent donor with phosphorescence at 605 nm. When secondary assembling with SC4AD, the phosphorescent emission peak of G⊂CB[8] generates a hypsochromic shift to 583 nm with a 6.4‐fold enhancement of intensity. Further, NIR fluorescence dyes Nile Blue (NiB) and Sulfo‐Cyanine 5 (cy5) are introduced to the assembly as acceptors to construct phosphorescent light‐harvesting systems. As expected, light‐harvesting systems with energy transfer efficiency of 57.5%/75.7% and a high antenna effect of 359.7/247.7 are constructed at an efficient donor/acceptor ratio of 100:1/15:2 for NiB and cy5, respectively. After co‐assembly with diarylethene derivative (1), the phosphorescence transferred from G⊂CB[8]@SC4AD/NiB (or cy5) to 1 and caused the photoluminescence quenching after irradiation by 365 nm light. And the photoluminescence of the light‐harvesting system was restored with the irradiation by >450 nm light. The highly efficient phosphorescent light‐harvesting system is applied to lysosome targeted imaging in HeLa cells and information encryption.

Cucurbit[8]uril-induced diarylethene thermally activated delay fluorescence supramolecular switch for sequential energy transfer

Constructing molecular switches based on supramolecular assembly strategy is a research hotspot. In this work, we constructed an all visible-light-regulated supramolecular photo-switch based on pyridinium-modified diarylethene derivative (DTE-Me) and cucurbit[8]uril (CB[8]). CB[8] not only accelerated the photochromic process under 365 nm ultraviolet light but also shifted the absorption of open formed DTE-Me to the visible region, which led to efficient photocyclization under 450 nm visible light irradiation, while DTE-Me and DTE-Me/CB[7] remained unchanged under the same irradiating condition. Moreover, the complexation with CB[8] could induce the strong thermally activated delayed fluorescence (TADF) of guest molecular at 550 nm, which further shifted to 670 nm through two-step sequential energy transfer with sulforhodamine B (SRB) and Cy5. This energy transfer process could also be regulated with visible light, and the application for information encryption was also demonstrated. This assembly provides a convenient approach to construct all visible light-regulated TADF photo-switch.

Near-Infrared Phosphorescent Switch of Diarylethene Phenylpyridinium Derivative and Cucurbit[8]uril for Cell Imaging.

Near-infrared (NIR) pure organic room-temperature phosphorescence (RTP) materials have received growing research interest due to their wide application in the fields of high-resolution bioimaging and luminescent materials. In this work, the authors report a macrocycle-confined pure organic RTP supramolecular assembly, which is constructed by diarylethene phenylpyridinium derivative (DTE-TP) and cucurbit[8]uril (CB[8]). Compared with CB[6] and CB[7], the larger cavity of CB[8] induces molecular folding and enhances the intramolecular charge transfer interactions, which leads to the obtained assembly emitting efficient NIR phosphorescence at 700nm. Due to the photochromism of the diarylethene core, the NIR phosphorescence is reversibly regulated by light irradiation at wavelengths of 365 and >600nm. Furthermore, cell-based experiments show that this supramolecular assembly is located in the lysosomes and displays a NIR phosphorescence at 650-750nm. In addition, by means of phosphorescence resonance energy transfer, the obtained assembly exhibits a red-shifted NIR emission at 817nm. This supramolecular phosphorescent switch provides a convenient path for the modular design of water-soluble pure organic room-temperature NIR phosphorescent materials.

A Highly Efficient Phosphorescence/Fluorescence Supramolecular Switch Based on a Bromoisoquinoline Cascaded Assembly in Aqueous Solution.

Despite ongoing research into photocontrolled supramolecular switches, reversible photoswitching between room‐temperature phosphorescence (RTP) and delayed fluorescence is rare in the aqueous phase. Herein, an efficient RTP‐fluorescence switch based on a cascaded supramolecular assembly is reported, which is constructed using a 6‐bromoisoquinoline derivative (G3), cucurbit[7]uril (CB[7]), sulfonatocalix[4]arene (SC4A4), and a photochromic spiropyran (SP) derivative. Benefiting from the confinement effect of CB[7], initial complexation with CB[7] arouses an emerging RTP signal at 540 nm for G3. This structure subsequently coassembles with amphiphilic SC4A4 to form tight spherical nanoparticles, thereby further facilitating RTP emission (≈12 times) in addition to a prolonged lifetime (i.e., 1.80 ms c.f., 50.1 µs). Interestingly, following cascaded assembly with a photocontrolled energy acceptor (i.e., SP), the efficient light‐driven RTP energy transfer occurs when SP is transformed to its fluorescent merocyanine (MC) state. Ultimately, this endows the final system with an excellent RTP–fluorescence photoswitching property accompanied by multicolor tunable long‐lived emission. Moreover, this switching process can be reversibly modulated over multiple cycles under alternating UV and visible photoirradiation. Finally, the prepared switch is successfully applied to photocontrolled multicolor cell labeling to offer a new approach for the design and fabrication of novel advanced light‐responsive RTP materials in aqueous environments.

A tunable phosphorescence supramolecular switch by an anthracene photoreaction in aqueous solution

A supramolecular phosphorescent switch, composed of a linear assembly formed by a photosensitive bromophenylpyridium derivative and cucurbit[8]uril, can respond to the dual stimulation of ultraviolet light and heating with good reversible stability.

Lanthanide Luminescence Supramolecular Switch Based on Photoreactive Ammonium Molybdate.

Lanthanide supramolecular assemblies as photoswitches have attracted much attention in the fields of cellular imaging and light-emitting materials. However, the regulation of lanthanide luminescence behavior by redox of metal ions is rare. Herein, we constructed a lanthanide luminescence supramolecular switch, that is, a binary assembly constructed by mono-(6-ethylenediamine-6-deoxy)-β-cyclodextrin (ECD) and ammonium molybdate tetrahydrate ((NH4)6Mo7O24·4H2O, Mo7), and further assembled into ternary assemblies with polyoxometalate Na9[XW10O36]·32H2O (X-POM, X = Eu and Dy), which was comprehensively characterized by UV-vis, fluorescence, NMR, Fourier transform infrared, dynamic light scattering, scanning electron microscopy, and ζ potential. Thanks to the oxygen-shielding effect of secondary supramolecular assembly, the photoreduction process of Mo7 (VI) could occur rapidly and efficiently. Due to the high Förster resonance energy transfer (FRET) efficiency of X-POM and Mo7 (V) in supramolecular assembly, the photoreduction process is accompanied by fluorescence quenching. In addition, the oxidation process of the Mo7 (V) could be rapidly promoted by heating, which allowed the X-POM fluorescence to recover. Interestingly, ECD-mediated ternary supramolecular assemblies not only tune the lanthanide luminescence but also strongly increase the lanthanide luminescence behavior, leading to the emission of strong narrow red light at 5D0-7F4, which can be successfully applied to two-dimensional code anticounterfeiting. In this study, a new approach is provided for the construction of lanthanide luminescence supramolecular switches tuned by photoreactive polyoxometalate.

Engineering a cationic supramolecular charge switch for facile amino acids enantiodiscrimination based on extended-gate field effect transistors

Chiral recognition of essential amino acids (EAAs) is a huge challenge that keeps plaguing analytical scientists due to their cryptochirality and limited steric interaction sites. Inspired by the superior enantioselectivity of functional supramolecular cyclodextrins (CDs) and strong signal amplification ability of field effect transistors (FETs), this work firstly reports a cationic supramolecular charge switch for facile enantiodiscrimination of EAAs based on extended-gate organic FET (EG-OFET). The cationic phenylcarbamoylated-CD single isomer acts as a charge switch via interacting with different enantiomers and the weak stereo-differentiation intermolecular interaction signals between the cationic perphenylcarbamoylated CDs and EAAs on the EG can be strongly and rapidly amplified through an OFET. Efficient chiral differentiation of six EAAs, including phenylalanine, tryptophan, leucine, isoleucine, lysine and valine, are successfully achieved without any derivation process and the detection limit for d-phenylalanine is down to 10−13 mol/L. We believe that this study provides a new and facile sensing perspective for natural amino acids and may afford deeper understanding of molecular chirality.

Highly Reversible Supramolecular Light Switch for NIR Phosphorescence Resonance Energy Transfer.

Although purely organic room‐temperature phosphorescence (RTP) has drawn widespread attention in recent years, regulatable phosphorescence resonance energy transfer (PRET) supramolecular switch is still rare. Herein, single molecular dual‐fold supramolecular light switches, which are constructed by phenylpyridinium salts modified diarylethene derivatives (DTE‐Cn, n = 3, 5) and cucurbit[8]uril (CB[8]) are reported. Significantly, biaxial [3]pseudorotaxane displayed efficiently reversible RTP after binding with CB[8] and the phosphorescence quenching efficiency is calculated up to be 99%. Furthermore, the binary supramolecular assembly can coassemble with Cy5 to form ternary supramolecular assembly showing efficiently PRET, which is successfully applied in switchable near infrared (NIR) mitochondria‐targeted cell imaging and photocontrolled data encryption. This supramolecular strategy involving energy transfer provides a convenient approach for phosphorescent application in biology and material fields.

Crystallographic Visualization of a Guest-Induced Solar-Driven Cycloaddition Reaction Based on a Recyclable Nonporous Coordination Polymer.

Stimuli-responsive solids with adjustable photophysical properties are particularly attractive because they can be used as smart materials in anticounterfeiting, information storage, holographic imaging, and other fields. Herein, we report a unique nonporous coordination polymer, {[Ag(3,3'-dpe)](2,2'-Hbpdc)}n (1; 3,3'-dpe = 1,2-dipyridin-3-ylethene and 2,2'-H2bpdc = 2,2'-biphenyldicarboxylic acid), that can convert to an extremely photoreactive compound, 1·H2O·MeCN (MeCN = acetonitrile), through guest capture. Upon irradiation of sunlight, 1·H2O·MeCN can transform to {[Ag(3,3'-tpcb)0.5](2,2'-Hbpdc)(H2O)(MeCN)}n (2·H2O·MeCN; 3,3'-tpcb = 1,2,3,4-tetrapyridin-3-ylcyclobutane). 2·H2O·MeCN can lose its solvent molecules to form 2 and further return to 1 at high temperature. Accompanied by direct visualization based on multistep single-crystal-to-single-crystal conversions, the recyclable crystalline solid exhibits remarkable fluorescence changes, which makes it a supramolecular switch for application in multiple anticounterfeiting.

PH/H2O2 Dual-Responsive Chiral Mesoporous Silica Nanorods Coated with a Biocompatible Active Targeting Ligand for Cancer Therapy.

Nano-drug delivery systems (nano-DDSs) with an existing specific interaction to tumor cells and intelligent stimulus-triggered drug delivery performance in a tumor microenvironment (TME) remain hotspots for effective cancer therapy. Herein, multifunctional pH/H2O2 dual-responsive chiral mesoporous silica nanorods (HA-CD/DOX-PCMSRs) were creatively constructed by first grafting phenylboronic acid pinacol ester (PBAP) onto the amino-functioned nanorods, then incorporating doxorubicin (DOX) into the mesoporous structure, and finally coating with the cyclodextrin-modified hyaluronic acid conjugate (HA-CD) through a weak host-guest interaction. Under a physiological environment, the gatekeeper CD could avoid the premature leakage of DOX and minimize the side effects to normal cells. After the uptake by the tumor cells, the H2O2-sensitive moieties of PBAP were exposed and a small amount of DOX was leaked along with the shift of the supramolecular switch HA-CD under the acidic condition. Notably, the self-supplying H2O2 mediated by the released DOX in turn accelerated the PBAP disintegration, further promoted the rapid release of DOX, and increased the DOX accumulation in tumor regions. Innovatively, this nano-DDS could simultaneously achieve the tumor-targeting ability via CD44 receptor-mediated endocytosis and pH/H2O2 dual responsiveness activated by the TME and hence exhibited superior antitumor efficacy. Furthermore, HA acting as the hydrophilic shell could improve the biocompatibility of this nano-DDS.