An Emission-Based Probe for the Detection and Quantification of DNA and RNA.

Sequence-independent detection of low concentrations of nucleic acids is important for applications in forensics and diagnostics. An emission-based probe for detecting and quantifying DNA and RNA utilizing a water-soluble dicationic tetraphenylethene (TPE) derivativewas developed. The recognition is based on the electrostatic and other non-covalent interactions between the phosphate backbone of nucleic acids and the cationic probe, which cause the restriction of rotation of the aryl units of the probe, ensuing in the enhancement of the fluorescence signal. The binding was validated by different spectroscopic techniques and also by electrophoretic mobility shift assay. The probable mode of binding with the nucleic acids was studied by blind-docking studies that correlated well with the experimental results.

Cyano disubstituted tetrabenzoindeno[2,1-a]fluorene: open-shell or closed-shell?

Organic diradicaloids have lately emerged as potential spintronic materials. We report the unprecedented synthesis of a near-IR absorbing indeno[2,1-a]fluorene derivative that displays remarkably low LUMO (-4.15 eV) and a small HOMO-LUMO gap (0.85 eV). NMR/EPR studies indicated its open-shell diradical property, which was supported by DFT calculations while suggesting a 30% diradical character and a small singlet (S)-triplet (T) gap (-2.52 kcal mol-1). A large bond length alternation of the as-indacene core for its single-crystals indicated a quinoidal contribution with greater antiaromaticity, which is in line with the small diradical character despite showing a small S-T gap.

Tuning properties of functionalized azobenzene photoswitches through variation of substitution and their position.

This perspective article features the recent work published in this journal on functionalized azobenzene photoswitches, studied by Venkataramani and coworkers [Grewal, S. et al (2024) Photochem. Photobiol., 1-16]. Azobenzene-based photochromic molecules undergo reversible trans-to-cis isomerization under exposure to light. The reverse cis-to-trans isomerization also takes place under thermal conditions in the dark. The study explores how different functional groups at various positions affect the responses of these compounds to light, their thermal stabilities, the isomeric ratios in the photostationary states, and their supramolecular behavior. Results show varied thermal half-lives, influenced by the terminal groups and their positions. Aggregation studies reveal the formation of supramolecular architectures, from microcrystals to gels with these systems. Despite complexities with the large volume of work with 30 different compounds, the research provides insights into designing efficient photochromic supramolecular motifs.

Morphology Tuning via Linker Modulation: Metal-Free Covalent Organic Nanostructures with Exceptional Chemical Stability for Electrocatalytic Water Splitting.

The development of synthetic routes for the formation of robust porous organic polymers (POPs) with well-defined nanoscale morphology is fundamentally significant for their practical applications. The thermodynamic characteristics that arise from reversible covalent bonding impart intrinsic chemical instability in the polymers, thereby impeding their overall potential. Herein, a unique strategy is reported to overcome the stability issue by designing robust imidazole-linked POPs via tandem reversible/irreversible bond formation. Incorporating inherent rigidity into the secondary building units leads to robust microporous polymeric nanostructures with hollow-spherical morphologies. An in-depth analysis by extensive solid-state NMR (1D and 2D) study on 1H, 13C, and 14N nuclei elucidates the bonding and reveals the high purity of the newly designed imidazole-based POPs. The nitrogen-rich polymeric nanostructures are further used as metal-free electrocatalysts for water splitting. In particular, the rigid POPs show excellent catalytic activity toward the oxygen evolution reaction (OER) with long-term durability. Among them, the most efficient OER electrocatalyst (TAT-TFBE) requires 314 mV of overpotential to drive 10 mA cm-2 current density, demonstrating its superiority over state-of-the-art catalysts (RuO2 and IrO2).

Light-driven modulation of electrical conductance with photochromic switches: bridging photochemistry with optoelectronics.

Photochromic conducting molecules have emerged because of their unique capacity to modulate electrical conductivity upon exposure to light, toggling between high and low conductive states. This unique amalgamation has unlocked novel avenues for the application of these materials across diverse areas in optoelectronics and smart materials. The fundamental mechanism underpinning this phenomenon is based on the light-driven isomerization of conjugated π-systems which influences the extent of conjugation. The photoisomerization process discussed here involves photochromic switches such as azobenzenes, diarylethenes, spiropyrans, dimethyldihydropyrenes, and norbornadiene. The change in the degree of conjugation alters the charge transport in both single molecules and bulk states in solid samples or solutions. This article discusses a number of recent examples of photochromic conducting systems and the challenges and potentials of the field.

Visible-light-switchable Chalcone-Flavylium Photochromic Systems in Aqueous Media.

The chalcone-flavylium photochromic system switches in aqueous media. However, the chalcone→flavylium conversion requires detrimental ultra-violet (UV) light for the switching which deters their applications in the biological domain. To address this issue, we have synthesized strategically modified chalcone scaffolds that can be reversibly switched to the flavylium forms with visible light ranging from 456 nm (blue) to 640 nm (red).

Stable Diradical on the Dimethyldihydropyrene Scaffold.

The diradical character in a molecular architecture can be customized primarily in two ways: first, by employing a quinoidal pro-aromatic system with net energy gained by aromatization that compensates for the energy required to generate the diradical species and, second, by employing an antiaromatic system having easily accessible triplet states that impart a diradical character. We have chosen a 14π aromatic framework, Boekelheide's dimethyldihydropyrene, and perturbed its aromaticity through the construction of its quinoidal form. The perturbed aromaticity was evident from the bond alteration in the X-ray diffraction structure, 1H nuclear magnetic resonance chemical shifts, and quantum chemical calculations. The aromaticity was restored as the system underwent a transition to the biradical structure centered on two exocyclic carbons. In addition, upon photoexcitation and without using an external reducing reagent, the diradical could be converted to a radical anion and dianion form easily when dimethylformamide was used as a solvent.

Detection of Sialic Acid and Imaging of Cell-Surface Glycan Using a Fluorescence-SERS Dual Probe.

Sialic acid (SA) is an acidic monosaccharide present in the human brain and body fluids in the form of N-acetylneuraminic acid. It is also a well-known cancer biomarker. For decades, it has remained a challenging task to design synthetic receptors for SA. However, mainly because of the interference from other sugars with the receptors, it was challenging to differentiate SA from other sugars. Here, we report the development of a two-component aggregation-induced emissive (AIE) probes that can interact with SA and other saccharides via noncovalent interactions with unique emission fingerprints. Analysis of the output signals enabled the reliable detection and clear discrimination of SA in the presence of other saccharides with high accuracy. Further, its potential application in cellular glycan mapping has been explored by fluorescence imaging and surface-enhanced Raman scattering with MDA-MB-231 breast cancer cells.

Highly Selective and Quantitative Point-of-Care Diagnostic Method for Adrenaline.

Adrenaline, also known as epinephrine, is a neurotransmitter/hormone that is an important target in diagnostics. Development of an effective method for detecting it in the presence of other neurotransmitters is a challenging task. The electrochemical and fluorescent techniques commonly used have low selectivity in distinguishing among catecholamines. Herein, a small-molecule organic probe with an activated furfural moiety is reported to exploit the nucleophilicity of epinephrine to generate a bright-colored donor-acceptor Stenhouse adduct. Among nine common neurotransmitters or their analogues, only epinephrine was found to generate a unique colour change discernible with the naked eye, whereas the other ones remain unaffected. Under various in-field detection conditions, including solution, droplet, and paper strip-based detection, the colour change were also noticeable. The low detection limit of 1.37 nM and a limit of quantitation of 4.37 nM were achieved with simple UV/Vis methods in addition to the sub-ppm level sensing under visual conditions with naked eyes. The probe could be used for practical colorimetric measurements as a point-of-care tool without any complex and expensive machinery, making this approach accessible to all. In addition, using a simple smartphone, the determination of epinephrine concentrations is possible by using machine-learning techniques.

Photoresponsive Small Molecule Enzyme Mimics.

Enzyme mimics emulate the catalytic activities of their natural counterparts. Light-responsive enzyme mimics are an emerging branch of biomimetic chemistry where the catalytic activities can be controlled reversibly by light. These light-responsive systems are constructed by incorporating a suitable photoswitchable unit around the active-site mimic. As these systems are addressable by light, they do not leave back any undesired side products, and their activation-deactivation can be easily controlled. Naturally, these systems have enormous potential in the field of on-demand catalysis. The synthetic light-responsive enzyme mimics are robust and stable under harsh conditions. They do not require special handling protocols like those for real enzymes and can be tailor-made for improved solubility in a variety of solvents. How the introduction of the light-responsive systems has offered a new-edge to the field of small-molecule enzyme mimic has been elaborated in this Mini-review. Recent breakthroughs in light-responsive enzyme-like systems have been highlighted. Finally, the current obstacles and future prospects of this field have been discussed.

Azobenzene-based Photochromic Delivery Vehicles for Ions and Small Molecules.

Molecular switches have been used as delivery vehicles for various molecular and ionic species. The ones that reversibly operate with light are arguably the best candidates for the purpose as they can be operated using light. The two states of these photoswitchable systems often possess remarkable differences in terms of their structural features and electronic properties. Photochromic systems with the appropriate embellishment of functionalities at suitable positions have thus been used as photoresponsive receptors. The use of light-driven alterations of the structural features has led to differential molecular recognition with these switchable host molecules. In this article, we discuss the use of such supramolecular systems as the delivery vehicles for ions and molecules that started with the pioneering work by Shinkai back in 1979. This review will explicitly cover the development from 2001 to 2022 with some past background and the future prospects of the field.

Mimicking the Energy Funnel of the Photosynthetic Unit Using a Dendrimer-Dye Supramolecular Assembly.

Photosynthesis involves light-harvesting complexes where an array of antenna pigment channels the absorbed solar energy to the reaction centre of a photosystem. This work reports a supramolecular dendrimer-dye assembly that mimics the natural light-harvesting mechanism. A dendrimeric molecule based on two-fluorophores has been constructed with three coumarin units at the end of three long arms and a 7-diethylaminocoumarin unit at the interior. The molecule self-aggregates in water into spherical micelles, which can encapsulate a rose-bengal dye (RB). On excitation, peripheral coumarin units shuttled the energy to the loaded RB dye reaction center via a two-step cascade resonance energy transfer (RET). The energy absorbed in the periphery is funnelled efficiently, resulting in a strong emission from the dye that resembles an energy funnel. The energy transfer cascade has been studied with both steady-state and time-resolved fluorescence spectroscopy. Molecular dynamics simulations of the self-assembled aggregates in water were also in agreement with the experimental observations.

Metal Ion Mediated Instant Z → E Isomerization of Azobenzene Macrocycles in the Absence of Light.

The classical photoswitch azobenzenes reversibly interconvert between the E- and the Z-isomers with light. Here, we report a pair of new macrocyclic azobenzenes characterized thoroughly by spectroscopic methods and single crystal X-ray diffraction structures, and one of the compounds displays a quantitative conversion of the E- to the Z-form. These compounds, besides their normal photoswitching behavior, display an unusual instant switching of the Z-form to the E-isomer in the presence of Cu2+ ions in the dark under 273 K. The Cu2+ complex can stay in the Z-form under constant UV radiation. However, it reverts to the E-form as soon as the exposure to the UV is ceased. The same phenomenon is also observed with Ag+ ions albeit it is a bit slower. This unusual instant switching of the azobenzene systems with metal ions prompted the detailed studies to unravel the reason behind this behavior.

A Photoregulated Racemase Mimic.

The racemase enzymes convert L-amino acids to their D-isomer. The reaction proceeds through a stepwise deprotonation-reprotonation mechanism that is assisted by a pyridoxal phosphate (PLP) coenzyme. This work reports a PLP-photoswitch-imidazole triad where the racemization reaction can be controlled by light by tweaking the distance between the basic residue and the reaction centre.

Light-Gated Modulation of Electronic Mobility of a Dihydropyrene-Based Photochromic Coordination Polymer.

Photo-induced modulation of electronic conductance has been achieved by employing an AgI-based two-dimensional coordination polymer (CP) having pyridine-functionalized photochromic dimethyldihydropyrene-cyclophanediene (DHP-CPD) π-switch. Both the coordination polymer and the organic photochromic core were characterized by single-crystal X-ray diffraction studies. The coordination polymer displayed an excellent conductance in the ON state of the switch in the closed form of DHP. Upon exposure to visible light, the π-switch in the CPD form loses its planarity, turning the switch OFF, which is reflected in the drastic reduction of the conductance. Exposure to UV light turns the switch back ON wherein the high electronic conductance of the polymer can be restored.

Switching the recognition ability of a photoswitchable receptor towards phosphorylated anions.

An azobenzene based photoswitchable macrocyclic receptor displays different binding affinities in its E and Z forms towards various phosphorylated coenzymes under physiological conditions with remarkable selectivity for ATP in the E-form and selectivity towards GTP in the photoisomerized Z-form. Linear discriminant analysis clearly separated the analytes using the E-form. An application of this method enabled monitoring the progress of enzymatic phosphorylation using a tyrosine kinase enzyme.

Formation or Cleavage of Rings via Sulfide-Mediated Reduction Offers Background-Free Detection of Sulfide.

A set of three highly selective probes for sulfide detection has been developed. Two novel mechanistic strategies for the detection, including (a) transformation of a pro-fluorophore into an active fluorophore and (b) destruction of a fused ring to activate a fluorophore, have been explored. The structural features of the probes including azido groups ("active" and "latent") and leaving groups (with or without being attached to the fluorophore) have been investigated. During the course of the mechanistic studies, the single-crystal structures of all the probes and the products were obtained. One of the probes proved to be superior in terms of its ability to detect sulfide in pure water via an in situ formation of a fluorophore from a nonfluorescent precursor. These cheap and easy-to-prepare probes offer practical applications of sulfide recognition in environmental water samples and in the ovaries of fruit flies. A detection and quantification method using one of these probes and analysis with a smartphone enabled nonspecialists to detect sulfide reliably.

Modulation of Electronic Mobility of a One-Dimensional Coordination Polymeric Molecular Wire with Light.

Metal ions often influence the photoswitching efficiency of a photochromic system. This article reports a one-dimensional polymer having cyclic azobenzenes coordinated to silver ions that are bridged by nitrates. The coordination polymer (CP-2) displays a photoresponsive behavior. The switching ability in the polymer form was faster compared to the parent azobenzene ligand without the metal ions. Azobenzenes are reported to be poorly conducting. Here, although the azobenzene ligand does not show significant electronic mobility, the coordination polymer (CP-2) displays a modest conductivity. The conductance in the cis form of the polymer is significantly higher compared to the trans form. Upon exposure to visible light, the cis form undergoes photoisomerization to the trans form with a drastic drop in the electronic mobility. The trans form can be reverted to the cis form thermally or by using UV light. Thus, this system offers a reversible control of the conductivity using light.

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.

A phototunable anion receptor for C-HX interactions with benzoate anions.

A supramolecular receptor consisting of two anthracene moieties with binding motifs for binding of benzoate anions is reported here. NMR studies indicate that the binding involves π-π interactions and CHX interactions. Upon exposure to >350 nm light, the receptor undergoes a [4 + 4] photoelectrocyclization restricting the access to the binding site for benzoate. The reverse reaction works in the presence of the dual stimuli of 254 nm light and the benzoate anions. The work thus demonstrates a light mediated dynamic control of the binding pocket of a supramolecular anion receptor.