Correction: Recent progress of core-substituted naphthalenediimides: highlights from 2010.

Correction for 'Recent progress of core-substituted naphthalenediimides: highlights from 2010' by Sheshanath V. Bhosale et al., Org. Biomol. Chem., 2012, 10, 6455-6468, https://doi.org/10.1039/C2OB25798J.

Expanding the scope of self-assembled supramolecular biosensors: a highly selective and sensitive enzyme-responsive AIE-based fluorescent biosensor for trypsin detection and inhibitor screening.

Trypsin, a pancreatic enzyme associated with diseases like pancreatic cancer and cystic fibrosis, requires effective diagnostic tools. Current detection systems seldom utilize macrocyclic molecules and tetraphenyl ethylene (TPE) derivative-based supramolecular assemblies, known for their biocompatibility and aggregation-induced emission (AIE) properties, for trypsin detection. This study presents an enzyme-responsive, AIE-based fluorescence 'Turn-On' sensing platform for trypsin detection, employing sulfated-ß-cyclodextrin (S-ßCD), an imidazolium derivative of TPE (TPE-IM), and protamine sulfate (PrS). The anionic S-ßCD and cationic TPE-IM formed a strongly fluorescent supramolecular aggregation complex in an aqueous buffer. However, PrS suppresses fluorescence because of its strong binding affinity with S-ßCD. The non-fluorescent TPE-IM/S-ßCD/PrS supramolecular assembly system exhibits trypsin-responsive properties, as PrS is a known trypsin substrate. Trypsin restores fluorescence in the TPE-IM/S-ßCD system through the enzymatic cleavage of PrS, correlating linearly with trypsin catalytic activity in the 0-10 nM concentration range. The limit of detection is 10 pM. This work contributes to the development of self-assembled supramolecular biosensors using charged TPE derivatives and ß-cyclodextrin-based host-guest chemistry, offering an innovative fluorescence 'Turn-On' trypsin sensing platform. The sensing system is highly stable under various conditions, selective for trypsin, and demonstrates potential for biological analysis and disease diagnosis in human serum. Additionally, it shows promise for the screening of trypsin inhibitors.

Fabrication of Mesoporous Materials Based on Supramolecular Self-Assembly of Guanosine Monophosphonate-Nickel Chloride (GMP-Ni) for High-Performance Hybrid Supercapacitors.

Supramolecular self-assembly of nickel chloride and guanosine mono-phosphonate (GMP) and nickel (Ni)-based GMP-Ni and their calcinated mesoporous electrode materials GMP-Ni-500 and GMP-Ni-700 at 500 and 700 °C, respectively, have been fabricated. GMP-Ni, GMP-Ni-500, and GMP-Ni-700 are examined for their supercapacitor performance in a three-electrode configuration. The electrochemical tests demonstrate the mesoporous battery-type nature of GMP-Ni-500 which exhibited a specific capacity (Cs) of about 289 C g-1 at 0.5 A g-1 current density. In addition, a cost-effective and simple asymmetric supercapacitor device has been fabricated with battery-type GMP-Ni-500 as a cathode material and capacitive-type activated carbon (AC) as an anodic material. In an operating voltage window of 0 to 1.5 V, hybrid supercapacitors (HSCs) based on GMP-Ni-500//AC exhibited a remarkable performance with a specific capacity (Cs) of 144 C g-1 at 0.5 A g-1. For the HSC device, the maximum of 66% capacity retention has been observed after 5000 charging/discharging cycles at 5 A g-1. Furthermore, the HSC device demonstrates a high energy density of 24 W h kg-1 at a power density of 297 W kg-1. The molecular transformation was established by employing theoretical calculations. These results suggest that our HSC has outstanding potential in technology development for next-generation commercial applications.

Synthesis, Photophysical Properties and Self-Assembly of a Tetraphenylethylene-Naphthalene Diimide Donor-Acceptor Molecule.

The development of new π-conjugated molecular structures with controlled self-assembly and distinct photophysical properties is crucial for advancing applications in optoelectronics and biomaterials. This study introduces the synthesis and detailed self-assembly analysis of tetraphenylethylene (TPE) functionalized naphthalene diimide (NDI), a novel donor-acceptor molecular structure referred to as TPE-NDI. The investigation specifically focuses on elucidating the self-assembly behavior of TPE-NDI in mixed solvents of varying polarities, namely chloroform: methylcyclohexane (CHCl3 : MCH) and chloroform: methanol (CHCl3 : MeOH). Employing a several analytical methodologies, including UV-Vis absorption and fluorescence emission spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and dynamic light scattering (DLS), these self-assembled systems have been comprehensively examined. The results reveal that TPE-NDI manifests as distinct particles in CHCl3 : MCH (fMCH =90 %), while transitioning to flower-like assemblies in CHCl3 : MeOH (fMeOH =90 %). This finding underscores the critical role of solvent polarity in dictating the morphological characteristics of TPE-NDI self-assembled aggregates. Furthermore, the study proposes a molecular packing mechanism, based on SEM data, offering significant insights into the design and development of functional supramolecular systems. Such advancements in understanding the molecular self-assembly new π-conjugated molecular structures are anticipated to pave the way for novel applications in material science and nanotechnology.

Donor-acceptor molecular architecture involving carbazole/pyrazine/anthraquinone units for efficient supercapacitor applications.

A donor-acceptor composed of two 3,6-di-tert-butyl-9H-carbazoles (DTCs) and fused pyrazine (Pyz; 1)-anthraquinone (AQ; 1) was successfully synthesized. The as-fabricated DTCz-Pyz-AQ/graphite foil (GF) electrode in supercapacitor (SC) applications exhibited excellent specific capacitance (Csp) of about 304. 37 F g-1 and 106.0 F g-1 at 0.5 A g-1 current density in three electrode and symmetric two electrode configurations of SC cells, respectively, accompanied by good cycling stability. The highest energy density of the SSC cell was found to be 15.94 W h kg-1 at 899.71 W kg-1 power density. As a proof of concept DTCz-Pyz-AQ/GF (D-A/GF) has great potential in energy storage (ES) applications.

Molecular nanoarchitectonics of proton triggered tetraphenylethylene-based detector: colorimetric, reversible, and intracellular pH.

In this paper, we designed, synthesized, and characterized 4,4',4'',4'''-(ethene-1,1,2,2-tetrayl)tetrakis(N,N-dimethylaniline) (1). Furthermore, UV-Vis absorbance and fluorescence emission studies reveal that 1 acts as a selective and sensitive probe for reversible acid-base sensing in solution as well as in the solid state. Nevertheless, the probe exhibited colorimetric sensing and intracellular fluorescent cell imaging of acid-base sensitive cells, making it a practical sensor with several potential applications in chemistry.

Naphthalenediimide-based nanoarchitectonics for a fluorescent chemosensor with highly selective and sensitive detection of cyanide ions.

A naphthalenediimide (NDI)-based highly potential chemosensor for the detection of cyanide has been synthesized successfully in several steps. The NDI-based probe displayed high selectivity and sensitivity towards cyanide ions in fluorescence 'turn-off' mode over other ions used in this study. The naked-eye, UV-vis absorbance and fluorescence methods are employed to investigate the sensing performance of probe 1 toward CN- ion detection. The limit of detection for CN- ions was calculated to be 4.11 × 10-7 M. Moreover, the Stern-Volmer quenching constant and fluorescence quenching efficiency of CN- ions were estimated to be 1.1 × 105 M and 88.81%, respectively. Job's plot showed a 1 : 1 stoichiometric complexation reaction between probe 1 and CN- ions. For practical applications, probe 1 was efficiently applied for the detection of CN- ions using a paper strip method.

Retraction: Hydrogen sulfate ion sensing in aqueous media based on a fused pyrimido benzothiazole derivative.

[This retracts the article DOI: 10.1039/C6RA01980C.].

Retraction: Dipyrrolyl-bis-sulfonamide chromophore based probe for anion recognition.

[This retracts the article DOI: 10.1039/C4RA04000G.].

Retraction: A phosphonic acid appended naphthalene diimide motif for self-assembly into tunable nanostructures through molecular recognition with arginine in water.

Retraction of 'A phosphonic acid appended naphthalene diimide motif for self-assembly into tunable nanostructures through molecular recognition with arginine in water' by Kamalakar P. Nandre et al., Chem. Commun., 2013, 49, 5444-5446, https://doi.org/10.1039/C3CC41259H.

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.

2H-Pyran-2-one-Functionalized Diketopyrrolopyrrole Dye: Design, Synthesis, and Explosives Sensor.

In this work, a 2H-pyran-2-one-functionalized diketopyrrolopyrrole (DPP) (coded as receptor 1) was designed, synthesized, and fully characterized by various spectroscopic methods. The physical properties of molecular architecture 1 were studied employing theoretical calculations. Receptor 1 was elegantly scrutinized for the sensing of explosive nitroaromatic compounds (NACs). Receptor 1 exhibited detection of nitro explosives, i.e., picric acid (PA), 2,4-dinitrophenol (DNP), and nitrophenol (NP), via the fluorescence quenching mechanism. The Stern-Volmer equation was employed to evaluate the effectiveness of the quenching process. It was found that 1 exhibited a detection limit of about 7.58 × 10-5, 8.35 × 10-5, and 9.05 × 10-5 M toward PA, DNP, and NP, respectively. The influence of interfering metal ions and anions on PA detection was investigated thoroughly. Furthermore, receptor 1-based low-cost fluorescent thin-layer chromatography (TLC) plates were developed for the recognition of PA.

Direct Arylation: A Greener Synthesis of Anthraquinone-Naphthalene diimide-Based Small Chromophores for Applications in Organic Thin Film Transistors.

In this paper, we report the design and synthesis of three naphthalene diimide- (NDI) and anthraquinone- (AQ) based organic chromophores derived from direct arylation reactions; NDI-AQ, AQ-NDI-AQ and NDI-AQ-NDI. Compared to classic cross-coupling reactions, this method reduced the number of synthetic and purification steps. The chemical structures, photophysical and electrochemical properties of these molecules were characterized using UV-vis spectroscopy, fluorescence emission spectroscopy and cyclic voltammetry (CV). The optoelectronic properties of the three dyes enabled the fabrication of organic thin film transistors (OTFTs). The fabricated OTFTs displayed good n-type semiconducting properties, with electron mobilities ( µ e ${{\mu }_{e}}$ ) of 1.5-4.2×10-4  cm2  V-1 s-1 .

Nanoarchitectonics of neomycin-derived fluorescent carbon dots for selective detection of Fe3+ ions.

The first-ever neomycin antibiotic-based carbon dots (Neo-CDs) were synthesized via a low-cost, eco-friendly, and single-step hydrothermal method using neomycin as a single precursor. The as-prepared Neo-CDs exhibited strong and stable blue fluorescence and were well characterized by TEM, UV-vis absorption, fluorescence emission, IR, XRD, Raman and XPS spectroscopy methods. The Neo-CDs showed a well-distributed size within the range of 4.5 to 7.8 nm, comprising various functional groups on the surface of the carbon core. The Neo-CDs exhibited exceptional emission behaviour, and fluorescence quantum yield was calculated to be 55% in double distilled water. Neo-CDs have been used as a fluorescent sensor for selective and sensitive detection of Fe3+ ions in aqueous solution in the fluorescence turn-off mode. From the set of metal ions, only the Fe3+ ion showed quenching of fluorescence due to photoinduced (PET) electron transfer from Neo-CDs to the half-filled 3d orbital of Fe3+ ions. The limit of detection for Fe3+ ions was calculated to be 0.854 µM. Further, the quenching efficiency and Stern-Volmer quenching constant have been calculated which are about 94% and 5.6 × 106 M-1, respectively.

Aminoglycoside antibiotic kanamycin functionalized tetraphenylethylene molecular probe for highly selective detection of bovine serum albumin protein.

A novel tetraphenylethylene (TPE) functionalized aminoglycoside antibiotic kanamycin (TPE-kana 1) has been successfully synthesized and characterized by means of modern analytical and spectroscopic techniques. The probe TPE-kana 1 showed strong affinity towards bovine serum albumin (BSA) compared to its other biological competitors. The recognition of BSA have been investigated employing UV-Vis absorption and fluorescence emission spectroscopy. The significant color change of TPE-kana 1 with BSA can be observed by necked eye, where the role of AIE-active TPE molecule is handle in both optical and colorimetric changes. The quenching of fluorescence of TPE-kana 1 with BSA was characterized by fluorescence spectroscopy, with 71.16% of quenching efficiency. Moreover, the Stern-Volmer quenching constant was calculated and found to be 2.46 × 107 M-1. Probe TPE-kana 1 showed detection limit of 2.87 nM (nM) towards BSA with binding constant 7.56 × 107 M. A molecular docking study is also performed to investigate the detail interactions between TPE-kana 1 with the sites of BSA via non-covalent i.e., H-bonding, π-cation interactions, π-donor hydrogen bonds and π-π interactions. The lowest binding energy conformation was found at - 10.42 kcal/mol.

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.

A cationic AIEgen and hexametaphosphate based simple and convenient fluorometric assay for alkaline phosphatase and its inhibitor.

Alkaline phosphatase (ALP) is an important biomarker to diagnose a number of diseases, such as anaemia, hepatobiliary diseases, chronic nephritis, and hypothyroidism. Therefore, the development of simple and convenient assays to monitor levels of ALP is highly desirable. In the present study, an aggregation-induced emission based simple, real-time, and direct fluorescence detection platform has been developed, by using a tetracationic pyridinium derivative of tetraphenylethylene (TPy-TPE) and anionic sodium hexametaphosphate (HMP) as component units. The sensing system, based on the TPy-TPE-HMP assembly, is highly responsive to the ALP dependent disintegration of the TPy-TPE-HMP aggregation complex, owing to HMP digestion by ALP. The sensing platform has an ALP detection limit of 16 mU mL-1 and linear range of 0-742 mU mL-1, respectively. The enzyme kinetic parameters, Km and Vmax, have been evaluated. In addition, the potential applicability of the TPy-TPE-HMP sensing system has also been shown with diluted human serum samples. Moreover, the TPy-TPE-HMP probe system is also useful for screening inhibitors of ALP.

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.

Correction: Dipyrrolyl-bis-sulfonamide chromophore based probe for anion recognition.

[This corrects the article DOI: 10.1039/C4RA04000G.].