Tetraphenylethylene-embedded pillar[5]arene-based orthogonal self-assembly for efficient photocatalysis in water.

Herein, we have designed and fabricated a simple and efficient supramolecular self-assembled nanosystem based on host-guest interactions between water-soluble tetraphenylethylene-embedded pillar[5]arene ( m -TPEWP5) and ammonium benzoyl-ʟ-alaninate (G) in an aqueous medium. The obtained assembly of m -TPEWP5 and G showed aggregation-induced emission (AIE) via the blocking of intramolecular phenyl-ring rotations and functioned as an ideal donor. After the loading of eosin Y (EsY) as acceptor on the surface of the assembly of m -TPEWP5 and G, the worm-like nanostructures changed into nanorods, which facilitates a Förster resonance energy transfer (FRET) from the m -TPEWP5 and G assembled donor to the EsY acceptor present in the nanorod assembly. The system comprising m -TPEWP5, G and EsY displayed moderate FRET efficiency (31%) at a 2:1 molar ratio of donor-to-acceptor. Moreover, the obtained supramolecular nanorod assembly could act as a nanoreactor mimicking natural photosynthesis and exhibited a high catalytic efficiency for the photocatalytic dehalogenation reaction of various bromoketone derivatives with good yields in short reaction time in water.

A photoswitchable "turn-on" fluorescent chemosensor: Quinoline-naphthalene duo for nanomolar detection of aluminum and bisulfite ions and its multifarious applications.

A quinoline-naphthalene duo-based Schiff base probe (R) was synthesized and characterized by the usual spectroscopic and single-crystal X-ray crystallographic techniques. Probe R detects Al3+ and HSO3- ions via the fluorescent turn-on approach by dual pathways i.e., i) when probe R interacts with Al3+, the restriction of CN single bond rotation, blocking of both photoinduced electron transfer (PET) and CN isomerization were observed, and ii) when the sensor R interacts with HSO3-, imine (CH = N) bond was cleaved via hydrolysis and produced the respective aldehyde and amine behaving as a chemodosimeter. The binding stoichiometric ratio of R + Al3+ (1:1) was confirmed by Job's plot, emission titration profile, NMR, and mass spectrometric analyses. This probe R is highly selective to both Al3+ -ions and HSO3- -ions, without any interference of other potentially competing cations and anions. Limit of detection (LOD) and quantification (LOQ) of R with Al3+ and HSO3- were downed to nanomolar concentrations, which is much lower than the recommended level of drinking water/food fixed by the World Health Organization (WHO). Furthermore, probe R was utilized in the detection of Al3+ and HSO3- ions in highly contaminated real samples, bioimaging in E. coli cells, multiple-targeting molecular logic gate, and in bovine serum albumin (BSA) binding.

Artificial light-harvesting systems based on macrocycle-assisted supramolecular assembly in aqueous media.

Light-harvesting, which involves the conversion of sunlight into chemical energy by natural systems such as plants, bacteria, is one of the most universal routine activities in nature. Thus far, various artificial light-harvesting systems (LHSs) have been fabricated toward solar energy utilization through mimicking natural photosynthesis in simplified and altered ways. Macrocycles are supramolecular hosts with unique cavities, in which specific guest molecules can be recognized based on non-covalent interactions. They have been widely employed in constructing LHSs due to their ability to form supramolecular assembly and dynamic molecular activity. In this review, we mainly focus on some representative examples reported by our group and other groups. Specifically, the fabrication of LHSs and their related discussions, such as a high donor/acceptor ratio, driving force for the formation of supramolecular assemblies and energy transfer mechanisms using different water-soluble macrocycles such as cyclodextrins (CD), pillararenes (PA), calixarenes (CA), cucurbiturils (CB), and other macrocycles will be included. In addition, how the resulting supramolecular self-assembled LHSs could be potentially utilized for photocatalysis, sensing, and imaging is also explained in detail. Challenges and developing trends for photochemical solar energy conversion will also be presented.

Graphene oxide-rhodamine nanocomposite for picomolar detection of chromium(III) by fluorimetry and its biofilm inhibition.

Graphene oxide-rhodamine B hydrazide (GO-RhB) nanocomposite was prepared by a simple chemical method and characterized by various spectroscopic and analytical techniques. GO-RhB nanocomposite potentially detects Cr3+ ion (excitation/emission = 550 nm/572 nm) via fluorescence turn "on-off" approach. This composite showed high binding affinity (106 M-1) with Cr3+ and a+ limit of detection (LOD) down to picomolar concentration (LOD = 85.6 pM). As far as we know, this is the first report for the sensing of Cr3+ ion at picomolar concentration. GO-RhB selectively senses Cr3+ ion without any interference of other coexisting metal ions. In addition, this composite exhibited the dynamic nature of quenching in the presence of Cr3+ ion, which is confirmed by the Stern-Volmer plot, fluorescence temperature profiles, and decay time experiments. The GO-RhB nanocomposite-based fluorescent probe was successfully applied to the quantitative detection of Cr3+ ion in milk sample (linear range = 2 to 10 nM) with better performance than other existing methods. Besides, this GO-RhB composite showed better antibiofilm activity against Acinetobacter baumannii and methicillin-resistant Staphylococcus aureus (MRSA) by using the Congo red agar and tube method.

Orthogonal Design of a Water-Soluble meso-Tetraphenylethene-Functionalized Pillar[5]arene with Aggregation-Induced Emission Property and Its Therapeutic Application.

An orthogonal strategy was utilized for synthesizing a novel water-soluble pillar[5]arene (m-TPEWP5) with tetraphenylethene-functionalized on the bridged methylene group (meso-position) of the pillararene skeleton. The obtained macrocycle exhibit both the aggregation-induced emission (AIE) effect and interesting host-guest property. Moreover, it can be made to bind with a tailor-made camptothecin-based prodrug guest (DNS-G) to form AIE-nanoparticles based on host-guest interaction and the fluorescence resonance energy transfer process for fabricating a drug delivery system. This novel type of water-soluble AIE-active macrocycle can serve as a potential fluorescent material for cancer diagnosis and therapy. In addition, the present orthogonal strategy for designing meso-functionalized aromatic macrocycles may pave a new avenue for creating novel supramolecular structures and functional materials.

Insight into functionalized-macrocycles-guided supramolecular photocatalysis.

Due to the unique characteristics of macrocycles (e.g., the ease of modification, hydrophobic cavities, and specific guest recognition), they can provide a suitable environment to realize photocatalysis via noncovalent interactions with different substrates. In this minireview, we emphasized the photochemical transformation and catalytic reactivity of different guests based on the binding with various macrocyclic hosts as well as on the role of macrocyclic-hosts-assisted hybrid materials in energy transfer. To keep the clarity of this review, the macrocycles are categorized into the most commonly used supramolecular hosts, including crown ethers, cyclodextrins, cucurbiturils, calixarenes, and pillararenes. This minireview not only summarizes the role that macrocycles play in photocatalytic reactions but also clarifies the photocatalytic mechanisms. Finally, the future research efforts and new pathways to apply macrocycles and supramolecular hybrid materials in photocatalysis are also discussed.

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.