Chaperone Mimetic Strategy for Achieving Organic Room-Temperature Phosphorescence based on Confined Supramolecular Assembly.

The development of organic materials that deliver room-temperature phosphorescence (RTP) is highly interesting for potential applications such as anticounterfeiting, optoelectronic devices, and bioimaging. Herein, a molecular chaperone strategy for controlling isolated chromophores to achieve high-performance RTP is demonstrated. Systematic experiments coupled with theoretical evidence reveal that the host plays a similar role as a molecular chaperone that anchors the chromophores for limited nonradiative decay and directs the proper conformation of guests for enhanced intersystem crossing through noncovalent interactions. For deduction of structure-property relationships, various structure-related descriptors that correlate with the RTP performance are identified, thus offering the possibility to quantitatively design and predict the phosphorescent behaviors of these systems. Furthermore, application in thermal printing is well realized for these RTP materials. The present work discloses an effective strategy for efficient construction of organic RTP materials, delivering a modular model which is expected to help expand the diversity of desirable RTP systems.

Tröger's Base-Based Cuboid Constructed by Chiral Self-Discrimination.

Cuboid, a basic geometric structure, has been widely applied in architecture and mathematics. In chemistry, the introduction of cuboid structures always provides a specific structural shape, enhances the stability of the structure and improves the performance of materials. Herein, a simple strategy exploiting self-discrimination to construct a cuboid-stacking crystal material is proposed, in which a chiral macrocycle (TBBP) based on Tröger's base (TB) and benzophenone (BP) was synthesized as the building element of the cuboid. The cuboid is designed to be transformable compared with cuboid structures in previous work. For this reason, it is considered that the cuboid-stacking structure can be transformed through external stimulation. Iodine vapor is selected as the external stimulus to transform the cuboid-stacking structure due to the favorable interaction between iodine and the cuboid. The changes in the stacking mode of TBBP is studied by single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD). To our surprise, this Tröger's base-based cuboid shows strong iodine adsorption capacity up to 3.43 g g-1 and exhibits potential as a crystal material for iodine adsorption.

Effective Iodine Capture Behavior by a Censer-shaped Macrocycle in Vapor Phase and Aqueous Solution.

Iodine capture is of great significance for disposal of the hazardous radioactive iodine. CTX[P(O)Ph], one kind of censer-shaped macrocycle cyclotrixylohydroquinoylene (CTX) derivatives, was applied as an efficient iodine adsorbent. It showed satisfactory iodine adsorption capacity in vapor phase and could be reused without obvious adsorption capacity loss. Besides, the adsorbent could also uptake iodine in water. Fortunately, two iodine loading CTX[P(O)Ph] crystal structures were obtained under different conditions to explore the mechanism of iodine adsorption. This work provides a relatively rare example of iodine adsorption by macrocycle. It is promising that the results with crystal information might be meaningful for exploring and designing new kinds of iodine adsorbents.

Square-Planar and Octahedral Gyroscope-Like Metal Complexes Consisting of Dipolar Rotators Encased in Dibridgehead Di(triaryl)phosphine Stators: Syntheses, Structures, Dynamic Properties, and Reactivity.

For a variety of purposes, it is of interest to embed metals in cagelike trans-spanning di(triaryl)phosphine ligands. Toward this end, a combination of P(p-C6H4O(CH2)mCH═CH2)3 [3; m = 4 (a), 5 (b), 6 (c), and 7 (d)], [Rh(COD)(µ-Cl)]2, and CO gives square-planar trans-Rh(CO)(Cl)[P(p-C6H4O(CH2)mCH═CH2)3]2 (4a-4d). Reactions of 4b-4d with Grubbs' catalyst (first generation) and then H2 (catalyst PtO2) yield the title compounds trans-Rh(CO)(Cl)[P(p-C6H4O(CH2)nO-p-C6H4)3P] (n = 2m + 2, 6b-6d; 26-41% from 4b-4d). Two are crystallographically characterized. The Cl-Rh-CO moieties rapidly rotate on the NMR time scale at -120 °C, per the ample clearance provided by the (CH2)n segments. Steric interactions with the PC6H4O linkages are analyzed. LiC≡CAr displaces the chloride ligand from 6b to give RhC≡CAr adducts (Ar = C6H5/p-C6H4CH3, 7b/8b). The ArC≡C-Rh-CO rotator of 7b rapidly rotates on the NMR time scale (-70 °C), but with 8b, the longer p-CH3C6H4C≡C group is confined between two (CH2)12 bridges, even at 120 °C. Reactions of Re(CO)5(X) and 3c (140 °C) give octahedral mer,trans-Re(CO)3(X)[P(p-C6H4O(CH2)6CH═CH2)3]2 (X = Cl/Br), and metathesis/hydrogenation sequences yield mer,trans-Re(CO)3(X)[P(p-C6H4O(CH2)14O-p-C6H4)3P]. Reactions of 6c and 6d and excess PMe3 give the free diphosphines P(p-C6H4O(CH2)nO-p-C6H4)3P (14c and 14d, 83-75%). The addition of 14d to [Rh(CO)2(µ-Cl)]2 reconstitutes 6d (87%). Both in,in and out,out isomers of 14c and 14d are possible, but low-temperature NMR spectra show one set of signals, consistent with rapid homeomorphic isomerizations that turn the molecules inside out. Thermolyses (C6D5Br, 140 °C) effect phosphorus inversion to give in,out isomers.

The Preparation of a Water-Soluble Phospholate-Based Macrocycle for Constructing Artificial Light-Harvesting Systems.

On the basis of cyclotrixylohydroquinoylene (CTX), a novel water-soluble phospholate-based CTX derivative (WPCTX) was prepared with facile synthetic procedure and satisfying yield. Several model guest molecules were selected to investigate WPCTX's host-guest properties. Based on the study of the host and model guest complexation, a tetraphenylethylene derivative from model guest was employed as a guest molecule (G) to form WPCTX⊃G nanoparticles (NPs) with WPCTX through further supramolecular self-assembly in water. Moreover, a hydrophobic fluorescent dye, Eosin Y(ESY) or Nile red (NiR), was encapsulated in WPCTX⊃G NPs to construct two types of artificial light-harvesting systems. Their high antenna effect demonstrated such NPs successfully mimicked light-harvesting systems in nature.

Multilevel Chirality Transfer from Amino Acid Derivatives to Circularly Polarized Luminescence-Active Nanoparticles in Aqueous Medium.

Chirality at different levels is widely observed in nature, but the clue to connect it all together, and the way chirality transfers among different levels are still obscure. Herein, a l-/d-lysine-based self-assembly system was constructed, in which two-step chirality transfer among three different levels was observed in aqueous solution. The chirality originated from the point chirality of amino acid derivatives l-/d-PyLys hydrochloride, and was transferred to the planar conformational chirality of water-soluble pillar[5]arene pR-/pS-WP5. Then, with the aid of pR-/pS-WP5, nanoparticles were formed that exhibited L-/R-handed circularly polarized luminescence with a dissymmetry factor of up to ±0.001, arising from pyrene chiral excimers. This multilevel chirality transfer not only provides a perspective to trace potential clues, and to pursue certain ways by which the chirality transfers, but also offers a strategy to create controllable CPL emission in aqueous media.

Selection of Planar Chiral Conformations between Pillar[5,6]arenes Induced by Amino Acid Derivatives in Aqueous Media.

Chiral α-amino acids play critical roles in the metabolic process in nearly all life forms. So far, chiral recognition of α-amino acids has mainly focused on the determination of l/d enantiomers. Herein, selection of planar chiral conformations between water-soluble pillar[5]arene WP5 and pillar[6]arene WP6 was observed due to α-side chain or ethyl ester moieties of l-α-amino acid ethyl ester hydrochlorides binding with WP5 and WP6, respectively. Therefore, α-side chain and ethyl ester moieties of l-α-amino acid ethyl ester hydrochlorides were recognized by observing the induced CD signal and its inversion. This is a rare example of being able to detect the chiral region around α-carbon of a chiral α-amino acid molecule.

Synthesis and Bioactivity of Guanidinium-Functionalized Pillar[5]arene as a Biofilm Disruptor.

Due to the inherent resistance of bacterial biofilms to antibiotics and their serious threat to global public health, novel therapeutic agents and strategies to tackle biofilms are urgently needed. To this end, we designed and synthesized a novel guanidinium-functionalized pillar[5]arene (GP5) that exhibited high antibacterial potency against Gram-negative E. coli (BH101) and Gram-positive S. aureus (ATCC25904) strains. More importantly, GP5 effectively disrupted preformed E. coli biofilms by efficient penetration through biofilm barriers and subsequent destruction of biofilm-enclosed bacteria. Furthermore, host-guest complexation between GP5 and cefazolin sodium, a conventional antibiotic that otherwise shows negligible activity against biofilms, exhibited much enhanced, synergistic disruption activity against E. coli biofilms, thus providing a novel supramolecular platform to effectively disrupt biofilms.

Role of Functionalized Pillararene Architectures in Supramolecular Catalysis.

The many useful features possessed by pillararenes (PAs; e.g. rigid, capacious, and hydrophobic cavities, as well as exposed functional groups) have led to a tremendous increase in their popularity since their first discovery in 2008. In this Minireview, we emphasize the use of functionalized PAs and their assembled supramolecular materials in the field of catalysis. We aim to provide a fundamental understanding and mechanism of the role PAs play in catalytic process. The topics are subdivided into catalysis promoted by the PA rim/cavity, PA-based nanomaterials, and PA-based polymeric materials. To the best of our knowledge, this is the first overview on PA-based catalysis. This Minireview not only summarizes the fabrications and applications of PAs in catalysis but also anticipates future research efforts in applying supramolecular hosts in catalysis.

Circularly polarized luminescent systems fabricated by Tröger's base derivatives through two different strategies.

The Tröger's base derivative rac-TBPP was synthesized and separated into two enantiomers R 2N -TBPP and S 2N -TBPP by chiral column chromatography. These compounds show a strong circularly polarized luminescence with g lum values of +0.0021, and -0.0025, respectively. The second way to fabricate the rac-TBPP-based CPL-active material is to co-gel the fluorescent rac-TBPP with a chiral ᴅ-glutamic acid gelator DGG by co-assembly strategy. At the molar ratio of rac-TBPP/DGG = 1:80, the g lum value of the co-gel was about three times higher than the g lum values of R 2N -TBPP and S 2N -TBPP enantiomers. Interestingly, the CPL handedness of the rac-TBPP/DGG co-gel could be adjusted effectively by changing their stoichiometric ratios.

Supramolecular Strategies for Controlling Reactivity within Confined Nanospaces.

Nanospaces are ubiquitous in the realm of biological systems and are of significant interest among supramolecular chemists. Understanding chemical behavior within nanospaces offers new perspectives on biological phenomena in nature and opens the way to highly unusual and selective forms of catalysis. Supramolecular chemistry exploits weak, yet effective, intermolecular interactions such as hydrogen bonding, metal-ligand coordination, and the hydrophobic effect to assemble nano-sized molecular architectures, providing reactions with remarkable rate acceleration, substrate specificity, and product selectivity. In this minireview, the focus is on the strategies that supramolecular chemists use to emulate the efficiency of biological processes, and elucidating how chemical reactivity is efficiently controlled within well-defined nanospaces. Approaches such as orientation and proximity of substrate, transition-state stabilization, and active-site incorporation will be discussed.

A Supramolecular Artificial Light-Harvesting System with Two-Step Sequential Energy Transfer for Photochemical Catalysis.

An artificial light-harvesting system with sequential energy-transfer process was fabricated based on a supramolecular strategy. Self-assembled from the host-guest complex formed by water-soluble pillar[5]arene (WP5), a bola-type tetraphenylethylene-functionalized dialkyl ammonium derivative (TPEDA), and two fluorescent dyes, Eosin Y (ESY) and Nile Red (NiR), the supramolecular vesicles achieve efficient energy transfer from the AIE guest TPEDA to ESY. ESY can function as a relay to further transfer the energy to the second acceptor NiR and realize a two-step sequential energy-transfer process with good efficiency. By tuning the donor/acceptor ratio, bright white light emission can be successfully achieved with a CIE coordinate of (0.33, 0.33). To better mimic natural photosynthesis and make full use of the harvested energy, the WP5⊃TPEDA-ESY-NiR system can be utilized as a nanoreactor: photocatalyzed dehalogenation of α-bromoacetophenone was realized with 96 % yield in aqueous medium.

Supramolecular vesicles based on pillar[n]arenes: design, construction, and applications.

Supramolecular vesicles have attracted considerable attention due to their advantages of facile construction, high-cargo-loading capacity, and good biocompatibility. Pillar[n]arenes are a unique family of supramolecular macrocycles, exhibiting excellent features and broad applications due to their intrinsic topology and high functionality. In the past decade, the construction of pillar[n]arene-based supramolecular vesicles has been continuously attempted and developed rapidly. In this review, we mainly summarize the significant advancements of such supramolecular vesicles in the last three years. By showing some representative examples, the design strategies, construction methods, and potential applications of these dynamic nanocarriers are discussed in detail. In particular, the responsiveness of such vesicles to various external stimuli and their applications in drug delivery are highlighted. The outstanding performance of pillar[n]arene-based supramolecular vesicles would definitely enrich the family of supramolecular vesicles and promote the development of dynamic supramolecular materials.

Multiresponsive Supramolecular Theranostic Nanoplatform Based on Pillar[5]arene and Diphenylboronic Acid Derivatives for Integrated Glucose Sensing and Insulin Delivery.

A closed-loop "smart" insulin delivery system with the capability to mimic pancreatic cells will be highly desirable for diabetes treatment. This study reports a multiple stimuli-responsive insulin delivery platform based on an explicit supramolecular strategy. Self-assembled from a well-designed amphiphilic host-guest complex formed by pillar[5]arene and a diphenylboronic acid derivative and loaded with insulin and glucose oxidase, the obtained insulin-GOx-loaded supramolecular vesicles can selectively recognize glucose, accompanied by the structure disruption and efficient release of the entrapped insulin triggered by the high glucose concentration as well as the in situ generated H2 O2 and acid microenvironment during the GOx-promoted specific oxidation of glucose into gluconic acid. Moreover, such a "smart" supramolecular theranostic nanoplatform is able to function as both a glucose sensor and a controlled insulin delivery actuator. In vivo experiments further demonstrate that this smart supramolecular nanocarrier shows fast response to hyperglycemic circumstances and can effectively regulate the glucose levels in a mouse model of type I diabetes.

From Supramolecular Vesicles to Micelles: Controllable Construction of Tumor-Targeting Nanocarriers Based on Host-Guest Interaction between a Pillar[5]arene-Based Prodrug and a RGD-Sulfonate Guest.

The targeting ability, drug-loading capacity, and size of the drug nanocarriers are crucial for enhancing the therapeutic index for cancer therapy. Herein, the morphology and size-controllable fabrication of supramolecular tumor-targeting nanocarriers based on host-guest recognition between a novel pillar[5]arene-based prodrug WP5-DOX and a Arg-Gly-Asp (RGD)-modified sulfonate guest RGD-SG is reported. The amphiphilic WP5-DOX⊃RGD-SG complex with a molar ratio of 5:1 self-assembles into vesicles, whereas smaller-sized micelles can be obtained by changing the molar ratio to 1:3. This represents a novel strategy of controllable construction of supramolecular nanovehicles with different sizes and morphologies based on the same host-guest interactions by using different host-guest ratios. Furthermore, in vitro and in vivo studies reveal that both these prodrug nanocarriers could selectively deliver doxorubicin to RGD receptor-overexpressing cancer cells, leading to longer blood retention time, enhanced antitumor efficacy, and reduced systematic toxicity in murine tumor model, suggesting their potential application for targeted drug delivery.

Formation of Twisted ß-Sheet Tapes from a Self-Complementary Peptide Based on Novel Pillararene-GCP Host-Guest Interaction with Gene Transfection Properties.

Small peptides capable of assembling into well-defined nanostructures have attracted extensive attention due to their interesting applications as biomaterials. This work reports the first example of a pillararene functionalized with a guanidiniocarbonyl pyrrole (GCP)-conjugated short peptide segment. The obtained amphiphilic peptide 1 spontaneously self-assembles into a supramolecular ß-sheet in aqueous solution based on host-guest interaction between pillararene and GCP unit as well as hydrogen-bonding between the peptide strands. Interestingly, peptide 1 at low concentration shows transitions from small particles to "pearl necklace" assemblies, and finally to branched fibers in a time-dependent process. At higher concentration, it directly assembles into twisted ß-sheet tapes. Notably, without pillararene moiety, the control peptide A forms α-helix structure with morphology changing from particles to bamboo-like assemblies depending on concentration, indicating a significant role of the pillararene-GCP host-guest interaction for the secondary structure formation. Moreover, peptide 1 can serve as an efficient gene transfection vector.

A Four-Armed Unsymmetrical Cryptand: From Two Different Host-Guest Interactions to Responsive Supramolecular Polymer.

By linking BMP32C10 and DB24C8 motifs together, a four-armed cryptand 1 is synthesized successfully, in which BMP32C10 motif can bind paraquat 2 while DB24C8 motif can complex dibenzylammonium salt 3 in spite of the electrostatic repulsion between guests 2 and 3. The base/acid-responsive supramolecular polymer is constructed further via two kinds of host-guest interactions between cryptand 1 and two homoditopic paraquat 4 and dibenzylammonium salt 5 similar to guests 2 and 3.

Highly Efficient Artificial Light-Harvesting Systems Constructed in Aqueous Solution Based on Supramolecular Self-Assembly.

Highly efficient light-harvesting systems were successfully fabricated in aqueous solution based on the supramolecular self-assembly of a water-soluble pillar[6]arene (WP6), a salicylaldehyde azine derivative (G), and two different fluorescence dyes, Nile Red (NiR) or Eosin Y (ESY). The WP6-G supramolecular assembly exhibits remarkably improved aggregation-induced emission enhancement and acts as a donor for the artificial light-harvesting system, and NiR or ESY, which are loaded within the WP6-G assembly, act as acceptors. An efficient energy-transfer process takes place from the WP6-G assembly not only to NiR but also to ESY for these two different systems. Furthermore, both of the WP6-G-NiR and WP6-G-ESY systems show an ultrahigh antenna effect at a high donor/acceptor ratio.

Asymmetric Michael addition reactions catalyzed by calix[4]thiourea cyclohexanediamine derivatives.

A number of upper rim-functionalized calix[4]thiourea cyclohexanediamine derivatives have been designed, synthesized and used as catalysts for enantioselective Michael addition reactions between nitroolefins and acetylacetone. The optimal catalyst 2 with a mono-thiourea group exhibited good performance in the presence of water/toluene (v/v = 1:2). Under the optimal reaction conditions, high yields of up to 99% and moderate to good enantioselectivities up to 94% ee were achieved. Detailed experiments clearly showed that the upper rim-functionalized hydrophobic calixarene scaffold played an important role in cooperation with the catalytic center to the good reactivities and enantioselectivities.

Glucose-Responsive Supramolecular Vesicles Based on Water-Soluble Pillar[5]arene and Pyridylboronic Acid Derivatives for Controlled Insulin Delivery.

The stimuli-responsive behavior of supramolecular nanocarriers is crucial for their potential applications as smart drug delivery systems. We hereby constructed a glucose-responsive supramolecular drug delivery system based on the host-guest interaction between a water-soluble pillar[5]arene (WP5) and a pyridylboronic acid derivative (G) for insulin delivery and controlled release under physiological conditions. The approach represents the ideal treatment of diabetes mellitus. The drug loading and in vitro drug release experiments demonstrated that large molecular weight insulin could be encapsulated into the vesicles with high loading efficiency, which, to our knowledge, is the first example of small-size supramolecular vesicles with excellent encapsulation capacity of a large protein molecule. Moreover, FITC-labeled insulin was used to evaluate the release behavior of insulin, and it was demonstrated that high glucose concentration could facilitate the quick release of insulin, suggesting a smart drug delivery system for potential application in controlled insulin release only under hyperglycemic conditions. Finally, we demonstrated that these supramolecular nanocarriers have good cytocompatibility, which is essential for their further biomedical applications. The present study provides a novel strategy for the construction of glucose-responsive smart supramolecular drug delivery systems, which has potential applications for the treatment of diabetes mellitus.