Mimicking the Natural World with Nanoarchitectonics for Self-Assembled Superstructures.

Scientists are often inspired by nature, where naturally occurring morphologies, such as those that resemble animals and plants, can be created in the lab. In this review, we have provided an overview on complex superstructures of animals, plants and some similar shapes from the natural world. We begin this review with a discussion about the formation of various animal-like shapes from small organic molecules and polymers, and then move onto plants and other selected shapes. Literature surveys reveal that most of the polymers studied tend to form micellar structures, with some exceptions. Nevertheless, small organic molecules tend to form not only micellar structures but also other animal shapes such as worms and caterpillars. These superstructures tend to have high surface areas and variable surface morphology, making them very useful material for applications in various field such as catalysis, solar cells, and biomedicine, amongst others.

A New 'Off-On' System Based on Core-Substituted Naphthalene Diimide with Dimethylamine for Reversible Acid-Base Sensing.

A new 'Off-On' system designed and synthesised by functionalisation of a naphthalene diimide (NDI) core with dimethylamine produces 4,9-bis(dimethylamino)-2,7-dioctylbenzo[lmn][3,8]-phenanthroline-1,3,6,8-(2H,7H)-tetraone, abbreviated as DDPT (1). DDPT 1 was synthesised using a simple strategy, namely aromatic nucleophilic substitution using Br2 -NDI with dimethylamine at 110 °C. DDPT was characterized by 1 H and 13 C NMR spectroscopy, ESI mass spectrometry and elemental analysis. DDPT 1 was then used for optical studies through protonation of its dimethylamine core with trifluoroacetic acid (TFA), blue-shifting the absorption band from 600 nm to 545 nm in solution. Interestingly, the fluorescence of DDPT 1 is weak in solution with a quantum yield Φ=0.09, which is significantly enhanced to Φ=0.78 upon addition of TFA. The limit of detection (LOD) was determined to 2.77 nm. Furthermore, DDPT 1 can be used for naked eyed detection not only under UV light (365 nm) but also using visible light, as clear changes can be clearly seen upon addition of TFA. The binding constant of DDPT was calculated to 2.1×10-3  m-1 . Importantly, DDPT 1 showed reversible switching by alternative addition of acid (TFA) and base (triethylamine) without loss of activity. Immobilised on paper, DDPT 1 can be used for strip-test sensing in which the colour changes from blue to reddish when expose to TFA vapours and reverse in the presence of triethylamine vapours.

Tetraphenylethene Derivatives Modulate the RNA Hairpin-G-Quadruplex Conformational Equilibria in Proto-oncogenes.

RNA G-quadruplex (GQs) sequences in 5'-UTRs of certain proto-oncogenes co-localize with hairpin (Hp) forming sequences resulting in intramolecular Hp-GQ conformational equilibria, which is suggested to regulate cancer development and progression. Thus, regulation of Hp-GQ equilibria with small molecules is an attractive but less explored therapeutic approach. Herein, two tetraphenylethene (TPE) derivatives, TPE-Py and TPE-MePy, were synthesized and their effect on Hp-GQ equilibrium was explored. FRET, CD and molecular docking experiments suggest that cationic TPE-MePy shifts the Hp-GQ equilibrium significantly towards the GQ conformer mainly through π-π stacking and van der Waals interactions. In the presence of TPE-MePy, the observed rate constant values for first and second folding steps were increased up to 14.6 and 2.6-fold, respectively. The FRET melting assay showed a strong stabilizing ability of TPE-MePy (ΔTm=4.36 °C). Notably, the unmethylated derivative TPE-Py did not alter the Hp-GQ equilibrium. Subsequently, luciferase assay analysis demonstrated that the TPE-MePy derivatives suppressed the translation efficiency by ∼5.7-fold by shifting the Hp-GQ equilibrium toward GQ conformers in the 5'-UTR of TRF2. Our data suggests that HpGQ equilibria could be selectively targeted with small molecules to modulate translation for therapy.

Polyanionic Cyclodextrin-Induced Supramolecular Assembly of a Cationic Tetraphenylethylene Derivative with Aggregation-Induced Emission.

The combination of supramolecular chemistry and aggregation-induced emission-based luminogens (AIEgens) has recently attracted tremendous attention because of its ability to offer large emission enhancement even in substantially dilute solutions. In this work, a new aggregation-induced emission (AIE)-based supramolecular assembly has been reported, which consists of a polyanionic cyclodextrin derivative and a tetracationic tetraphenylethylene (TPE) derivative. Ionic cyclodextrins have attracted significant attention in host-guest supramolecular chemistry and pharmaceutical industry. However, ionic derivatives of ß-cyclodextrins have not been explored to establish noncovalent interactions-based aggregation assembly of the most popular class of AIEgens, i.e., tetraphenylethylene derivatives. The current report demonstrates AIE of a tetracationic methyl pyridinium derivative of tetraphenylethylene (TPy-TPE) induced by a polyanionic sulfated ß-cyclodextrin (S-ßCD). The AIE-based supramolecular assembly has been thoroughly investigated using steady-state fluorescence, ground-state absorbance, and time-resolved fluorescence measurements. Further, the response of the supramolecular assembly towards external stimuli, such as, ionic strength, pH, and temperature, has been investigated. In addition, the complexation behavior of the TPE derivative has also been compared with the native neutral ß-cyclodextrin derivative, which delineates the important role of the negatively charged portal of S-ßCD in inducing aggregation of the TPy-TPE. The stoichiometry of the complex has been found to be 3:1 for TPy-TPE:S-ßCD, using Job's plot analysis. Finally, to get insights into the underlying interactions between the supramolecular assembly components, molecular docking calculations have been performed.

Aggregation-Induced Emission-Based Material for Selective and Sensitive Recognition of Cyanide Anions in Solution and Biological Assays.

Cyanide is one of the highly poisonous pollutants to our environment and toxic to human health. It is important to develop the widely applicable methods for their recognition to secure safe uses for people coming into contact and handling cyanide and their derivatives. In this regard, the aggregation-induced emission materials possess high potential for the development of simple, fast, and convenient methods for cyanide detection through either "turn-off" or "turn-on". Among the AIE-based materials, tetraphenylethylene is a promising sensor for various sensing applications. In this paper, we have designed and synthesized a TPE-based chemosensor, which shows high sensitivity and displays good selectivity for cyanide (CN-) over others in the presence of interfering Cl-, I-, F-, Br-, HSO4 -, H2PO4 -, NO3 -, HCO3 -, and ClO4 - anions employed. The naked-eye, UV-vis, and fluorescence methods are employed to evaluate the performance of probe 1 toward CN- detection. From these experiments, CN- ions can be detected with a limit of detection as low as 67 nM, which is comparatively lower than that of the World Health Organization (WHO) permissible limit of the cyanide anion, that is, 1.9 µM. From the Job's plot, the 1:1 stoichiometric complexation reaction between probe 1 and CN- was found. The probe was efficiently applied for the detection of CN- ions using a paper strip method. The probe 1 also showed the potential of detecting CN- ions in various food items and in the cell line.

Aggregation Induced Emissive Luminogens for Sensing of Toxic Elements.

The major findings in the growing field of aggregation induced emissive (AIE) active materials for the detection of environmental toxic pollutants have been summarized and discussed in this Review article. Owing to the underlying photophysical phenomenon, fluorescent AIE active molecules show more impact on sensing applications. The major focus in current research efforts is on the development of AIE active materials such as TPE based organic fluorescent molecules, metal organic framework, and polymers that can be employed for the detection of toxic pollutants such as CN- , NO2- , Hg2+ , Cd2+ , As3+ , As5+ , F- , Pb2+ , Sb3+ ions.

Tuning Achiral to Chiral Supramolecular Helical Superstructures.

The design and synthesis of achiral organic functional molecules which can assemble into a chiral with selective handedness in the absence of chiral substances is an important in understanding the role chirality plays within these systems. In this review, we described general approaches towards supramolecular chiral molecules the synthesis and self-assembly of achiral molecule to active chiral molecules to investigate controlled supramolecular chiral nanostructures with their photoluminescent properties for rapid, sensitive and selective detection of analytes of choice. Various small molecules have been discussed for achiral to chiral along with induction of chirality and controlled chiral helical structures in detail. We discussed few examples where stimuli used to control the chirality such as temperature, pH etc. Finally, we will also explore on the photo responsive helicity properties of the aggregation induced emission active molecule such as tetraphenylethene conjugates.

Light triggered encapsulation and release of C60 with a photoswitchable TPE-based supramolecular tweezers.

Stimuli responsive hosts for C60 can control its binding and release on demand. A photoswitchable TPE based supramolecular host can encapsulate C60 in the Z-form with a markedly different visual change in the colour. In addition, the Z-1 bound C60 has been characterized by various spectroscopic methods and mass spectrometry. Upon exposure to visible light (>490 nm), the host switches to the E-form where the structural complementarity with the guest is destroyed as a result of which the C60 is disassembled from the host. The results described herein reveals an actionable roadmap to pursue further advances in component self-assembly particularly light-induced association and dissociation of a guest molecule.

Meet the Board of ChemistryOpen: Sheshanath†V. Bhosale.

Sheshanath V. Bhoslae received his PhD from Freie University Berlin (Germany) in supramolecular chemistry under the supervision of Prof. J. H. Fuhrhop in 2004. He then pursued his postdoctoral studies with Prof. S. Matile at University of Geneva (Switzerland) under the auspices of a Roche Foundation Fellowship. This was followed by a stay at Monash University (Australia) for 5 years as an ARC-APD Fellow. He worked at RMIT University, Melbourne (Australia) for 6 years as ARC-Future Fellowship. Currently, Prof. Bhosale is working at the Department of Chemistry, Goa University (India) as a UGC-FRP Professor, His research interests lie in the design and synthesis of π-functional materials, especially small molecules, for sensing, biomaterials, and supramolecular chemistry applications. So far, Prof. Bhosale has produced 185 research articles and his work has been cited more than 4400 times, giving him an h-index of 32. He currently serves as an active Editorial Board member for ChemistryOpen.