Boron- and Oxygen-Doped π-Extended Helical Nanographene with Circularly Polarised Thermally Activated Delayed Fluorescence.

Helical nanographenes have garnered substantial attention owing to their finely adjustable optical and semiconducting properties. The strategic integration of both helicity and heteroatoms into the nanographene structure, facilitated by a boron-oxygen-based multiple resonance (MR) thermally activated delayed fluorescence (TADF), elevates its photophysical and chiroptical features. This signifies the introduction of an elegant category of helical nanographene that combines optical (TADF) and chiroptical (CPL) features. In this direction, we report the synthesis, optical, and chiroptical properties of boron, oxygen-doped Π-extended helical nanographene. The π-extension induces distortion in the DOBNA-incorporated nanographene, endowing a pair of helicenes, (P)-B2NG, and (M)-B2NG exhibiting circularly polarized luminescence with glum of -2.3×10-3 and +2.5×10-3, respectively. B2NG exhibited MR-TADF with a lifetime below 5 µs, and a reasonably high fluorescence quantum yield (50 %). Our molecular design enriches the optical and chiroptical properties of nanographenes and opens up new opportunities in multidisciplinary fields.

Chiroptically active copper clusters as platform for enantioselective detection of lysine.

Metal clusters have drawn considerable research attention over the years due to their fascinating optical properties. Owing to their appealing photophysical characteristics, these materials have drawn attention as potential candidates for various application in diverse fields, including disease detection, biosensing, chemical sensing, and the fabrication of light-harvesting materials. Presently, there is an increasing research focus on the use of clusters in biomedical research, both as biodetection platform and as bioimaging agents. Of special interest are chiral clusters, which can selectively interact with chiral biomolecules owing to their optical activity. Herein, we showcase the use of a pair of chiroptically active copper clusters for the enantioselective detection of lysine, an amino acid of vast biological relevance. Two techniques are concurrently employed for the detection of lysine at varying concentrations. Circular dichroism serves as a potent tool for detecting lysine at low concentrations, whereas luminescence is effectively employed as a detection method for high analyte concentrations. The combined electronic impact of clusters and lysine resulted in the emergence of an enhanced enantioselective Cotton effect at specific wavelength.

Surfactant Directed Synthesis of Intrinsically Chiral Plasmonic Nanostructures and Precise Tuning of their Optical Activity through Controlled Self-Assembly.

Fabrication and transmission of plasmonic chirality is a rapidly developing area of research. While nanoscale chirality is reasonably well explored, research on intrinsically chiral nanostructures, that has ramifications to origin of homochirality, is still in its infancy. Herein, we report the synthesis of dog-bone shaped chiral gold nanostructures using a chiral cationic surfactant with excess ascorbic acid. Chiral growth is attributed to the specific binding and structure breaking ability of chiral surfactant and ascorbic acid. The controlled assembly of particles facilitated tuning and enhancement of chiral signals. Experimental observations were validated with theoretical simulations modelled in frequency domain with a surface integral-equation parameterization. Work highlighting the generation and tuning of plasmonic chirality provides new insights into the understanding of intrinsic chirality and paves way for their application in enantioselective catalysis and biosensing.

Detection of amyloid fibrils in Parkinson's disease using plasmonic chirality.

Amyloid fibrils, which are closely associated with various neurodegenerative diseases, are the final products in many protein aggregation pathways. The identification of fibrils at low concentration is, therefore, pivotal in disease diagnosis and development of therapeutic strategies. We report a methodology for the specific identification of amyloid fibrils using chiroptical effects in plasmonic nanoparticles. The formation of amyloid fibrils based on α-synuclein was probed using gold nanorods, which showed no apparent interaction with monomeric proteins but effective adsorption onto fibril structures via noncovalent interactions. The amyloid structure drives a helical nanorod arrangement, resulting in intense optical activity at the surface plasmon resonance wavelengths. This sensing technique was successfully applied to human brain homogenates of patients affected by Parkinson's disease, wherein protein fibrils related to the disease were identified through chiral signals from Au nanorods in the visible and near IR, whereas healthy brain samples did not exhibit any meaningful optical activity. The technique was additionally extended to the specific detection of infectious amyloids formed by prion proteins, thereby confirming the wide potential of the technique. The intense chiral response driven by strong dipolar coupling in helical Au nanorod arrangements allowed us to detect amyloid fibrils down to nanomolar concentrations.

Environmentally responsive plasmonic nanoassemblies for biosensing.

Assemblies of plasmonic nanoparticles enable new modalities for biosensing. Engineered superstructures from metal nanoparticles can enhance the plasmon resonances and chiroptical activity of nanoscale dispersions. Such phenomena are keys to the fabrication of highly sensitive, selective and fast-responding detection platforms, making them promising candidates for clinical applications. This tutorial review summarizes and discusses recent advances in this area. The topics covered in the review include the basic strategies adopted for assembly and engineering of plasmonic nanoparticles, optical properties of the assembled nanostructures and their applications to both in vitro and in vivo detection of biological compounds. We also offer our vision of the future prospects of this field of research. Among emerging applications in this area are novel nanosensors and platforms, for food safety, environmental monitoring, health safeguarding, as well as biodefense.

Bis(dipyrrinato)zinc(II) Complex Chiroptical Wires: Exfoliation into Single Strands and Intensification of Circularly Polarized Luminescence.

One-dimensional (1D) coordination polymers (CPs) experiences limitations in exfoliation into individual strands, which hamper their utility as functional 1D nanomaterials. Here we synthesize chiral 1D-CPs that feature the bis(dipyrrinato)zinc(II) complex motif. They can be exfoliated into single strands upon sonication in organic media, retaining lengths of up to 3.19 µm (ca. 2600 monomer units). Their chiroptical structure allows the exfoliated wires to show circularly polarized luminescence at an intensity 5.9 times that of reference monomer complexes.

Enantioselective Light Harvesting with Perylenediimide Guests on Self-Assembled Chiral Naphthalenediimide Nanofibers.

Self-assembling molecular systems often display amplified chirality compared to the monomeric state, which makes the molecular recognition more sensitive to chiral analytes. Herein, we report the almost absolute enantioselective recognition of a chiral perylenediimide (PDI) molecule by chiral supramolecular nanofibers of a bichromophoric naphthalenediimide (NDI) derivative. The chiral recognition was evaluated through the Förster resonance energy transfer (FRET) from the NDI-based host nanofibers to the guest PDI molecules. The excitation energy was successfully transferred to the guest molecule through efficient energy migration along the host nanofiber, thus demonstrating the light-harvesting capability of these hybrid systems. Furthermore, circularly polarized luminescence (CPL) was enantioselectively sensitized by the guest molecule as the wavelength band and sign of the CPL signal were switched in response to the chiral guest molecule.

Two-Step Synthesis of Boron-Fused Double Helicenes.

Novel boron-fused double [5]helicenes were synthesized from hexabromobenzene in two steps via Hart reaction and demethylative cyclization. The parent helicene shows excellent ambipolar conductivity, which can be explained by unique 3D π-stacking with a brickwork arrangement. Moreover, the introduction of four tert-butyl groups suppresses racemization, enabling optical resolution. The enantiomerically pure helicene shows deep blue fluorescence with Commission Internationale de l'Eclairage coordinates of (0.15, 0.08) and circularly polarized luminescence activity.

Self-discriminating termination of chiral supramolecular polymerization: tuning the length of nanofibers.

Directing the supramolecular polymerization towards a preferred type of organization is extremely important in the design of functional soft materials. Proposed herein is a simple methodology to tune the length and optical chirality of supramolecular polymers formed from a chiral bichromophoric binaphthalene by the control of enantiomeric excess (ee). The enantiopure compound gave thin fibers longer than a few microns, while the racemic mixture favored the formation of nanoparticles. The thermodynamic study unveils that the heterochiral assembly gets preference over the homochiral assembly. The stronger heterochiral binding over homochiral one terminated the elongation of fibrous assembly, thus leading to a control over the length of fibers in the nonracemic mixtures. The supramolecular polymerization driven by π-π interactions highlights the effect of the geometry of a twisted π-core on this self-sorting assembly.

Inversion of supramolecular chirality in bichromophoric perylene bisimides: influence of temperature and ultrasound.

The supramolecular helicity in the self-assembled nanostructures of two perylene bisimide bichromophoric systems could be controlled by varying the preparatory methods. The self-assembly of the compounds under different conditions was investigated in detail by using absorption, fluorescence, CD, FTIR, XRD, TEM, and SEM techniques. These studies reveal that the heating-cooling method results in aggregates with ordered molecular packing and enhanced optical chirality. Ultrasonication leads to molecular aggregates with less ordered packing wherein the supramolecular chirality was reversed relative to the sample prepared via a heating-cooling method. This heating-cooling method proved to be superior in terms of nanofiber synthesis, yielding fibers with extended length and a prominent helical twist. At higher concentration, both compounds exhibited a gelation property in benzonitrile. The tunable chiroptical properties in these supramolecular systems make them potential candidates for applications in the field of optical and electronic device fabrication based on organic nanostructures.

Clustering triggered emissive liquid crystalline template for dual mode upconverted and downconverted circularly polarized luminescence.

Liquid crystalline materials have attracted significant attention in chiroptical research due to their ability to form long range ordered helical superstructures. Research focus has been on exploiting the unique properties of liquid crystalline materials to demonstrate highly dissymmetric circularly polarised luminescent (CPL) systems. In this study, we present a thermally driven, facile approach to fabricate CPL-active materials utilizing cholesteryl benzoate as the active substrate. Cholesteryl benzoate, a well-known thermotropic liquid crystal, has been found to manifest intriguing optical characteristics upon subjecting to repeated heating-cooling cycles. Despite the absence of conventional fluorescent moieties, the material exhibited luminescence through aggregation induced clustering triggered emission mechanism. Systematic investigations revealed excitation-dependent CPL for solid cholesteryl benzoate films when subjected to multiple thermal cycles. The excited state chiroptical investigation performed after multiple thermal cycles showed a luminescence anisotropy (glum) of 8 × 10-2, which is a high value for simple organic molecules. Moreover, upon co-assembly with lanthanide-based upconversion nanophosphors (UCNPs), the hybrid system demonstrated upconverted circularly polarised luminescence (UC-CPL). Benefiting from the ability to endow upconversion nanoparticles of various sizes, fabrication of UCNP-ChB hybrid nanocomposites exhibiting multicoloured upconversion CPL was demonstrated. These findings highlight the potential of liquid crystalline materials for diverse applications, including 3D optical displays and anticounterfeiting technologies.

Engineering copper plasmonic chirality via ligand-induced dissolution for enantioselective recognition of amino acids.

The formation of chiral nanosystems and their subsequent enantioselective interaction with chiral amino acids are vital steps in many biological processes. Due to their potential to mimic biological systems, the synthesis of chiral nanomaterials has garnered significant attention over the years. Despite the emergence of diverse nanomaterials showcasing strong chiral responses, the in-depth understanding of the mechanism of plasmonic chirality in copper nanoparticles and their subsequent application in various fields are least explored. Herein, we demonstrate a facile approach for the synthesis of chiral copper nanoparticles using cysteine as a chiral precursor and capping ligand. Ligand-mediated chiral induction, established through experimental findings and a theoretical model, is ascribed as the major contributor to the origin of plasmonic chirality. The enantioselective recognition of chiral copper nanoparticles towards histidine, an amino acid with vast biological functions, was meticulously investigated by leveraging the strong copper-histidine binding ability. Ligand-induced dissolution, a unique phenomenon in nanoparticle reactions, was identified as the underlying mechanism for the nanoparticle-to-complex conversion. Understanding the mechanism of chiral induction in copper nanoparticles coupled with their enantioselective recognition of biomolecules not only holds promise in biomedical research but also sheds light on their potential as catalysts for asymmetric synthesis.

Aggregation-induced generation of circularly polarized luminescence in naphthaleneimide-based nanostructures with high dissymmetry factor.

Extensive efforts have been dedicated towards designing new organic materials that display solid-state fluorescence and possess optical activity, thereby leading to the fabrication of materials emitting circularly polarized light. Existing organic materials usually suffer from two limitations, a low dissymmetry factor (glum) and weak or no fluorescence in the solid state. Herein, we have demonstrated a naphthalene imide-based dyad system that remains fluorescent even in powder form and displays circularly polarized luminescence in its aggregated and solid state with significantly high glum values.

Circularly polarized luminescence in supramolecular assemblies of chiral bichromophoric perylene bisimides.

Chiral bichromophoric perylene bisimides are demonstrated as active materials of circularly polarized emission. The bichromophoric system exhibited circularly polarized luminescence with dissymmetry factors typical of that of similar organic chiral chromophoric systems in the monomeric state. Variation in solvent composition led to the formation of stably soluble helical aggregates through intermolecular interactions. A large enhancement in the dissymmetry of circularly polarized luminescence was exhibited by the aggregated structures both in the solution and solid states. The sum of excitonic couplings between the individual chromophoric units in the self-assembled state results in relatively large dissymmetry in the circularly polarized luminescence, thereby giving rise to enhanced dissymmetry factors for the aggregated structures. The spacer between chiral center and chromophoric units played a crucial role in the effective enhancement of chiroptical properties in the self-assembled structures. These materials might provide opportunities for the design of a new class of functional bichromophoric organic nanoarchitectures that can find potential applications in the field of chiroptical memory and light-emitting devices based on supramolecular electronics.

Surface plasmon coupling in end-to-end linked gold nanorod dimers and trimers.

Colloidal gold nanorods were aligned end-to-end via dithiol coupling. The scattering properties of the resultant nanostructures were investigated at the single particle level by combining dark-field microscopy and high resolution scanning electron microscopy. The longitudinal surface plasmon resonance of end-to-end coupled Au nanorods exhibited a red-shift as the number of rods in the chain increased. The nanostructures exhibited polarization-dependent optical properties, due to selective excitation of collective bonding and anti-bonding modes. The surface plasmon peak energy was not strongly dependent on the angle of rod-sphere-rod trimers. The experimental scattering spectra were compared with the results obtained from theoretical calculations using the Finite Element Method (FEM) and found to be in good agreement.

Delayed luminescence guided enhanced circularly polarized emission in atomically precise copper nanoclusters.

Metal nanoclusters, owing to their intriguing optical properties, have captivated research interest over the years. Of special interest have been chiral nanoclusters that display optical activity in the visible region of the electromagnetic spectrum. While the ground state chiral properties of metal nanoclusters have been reasonably well studied, of late research focus has shifted attention to their excited state chiral investigations. Herein, we report the synthesis and chiral investigations of a pair of enantiomerically pure copper nanoclusters that exhibit intense optical activity, both in their ground and excited states. The synthesis of nanoclusters using l- and d-isomers of the chiral ligand led to the formation of metal clusters that displayed mirror image circular dichroism and circularly polarized luminescence signals. Structural validation using single crystal XRD, powder XRD and XPS in conjunction with chiroptical and computational analysis helped to develop a structure-property correlation that is unique to such clusters. Investigations on the mechanism of photoluminescence revealed that the system exhibits long excited state lifetimes. A combination of delayed luminescence and chirality resulted in circularly polarized delayed luminescence, a phenomenon that is rather uncommon to the field of metal clusters. The chiral emissive properties could be successfully demonstrated in free-standing polymeric films highlighting their potential for use in the field of data encryption, security tags and polarized light emitting devices. Moreover, the fundamental understanding of the mechanism of excited state chirality in copper clusters opens avenues for the exploration of similar effects in a variety of other clusters.

Dual emissive optically active gold nanoclusters endowed with circularly polarized phosphorescence.

Enantiomerically pure Au nanoclusters exhibiting dual-emission corresponding to fluorescence and phosphorescence were synthesized by adopting a facile approach. Chiral luminescence was observed for the triplet emission leading to circularly polarized phosphorescence, both in solution and in solid states. The nanoclusters exhibited aggregation induced emission, and the aggregated clusters exhibited chiral phosphorescence.

Transmitting biomolecular chirality into carbon nanodots: a facile approach to acquire chiral light emission at the nanoscale.

Since the observation of chirality at the nanoscale, research focused towards the design and synthesis of optically active nanomaterials has been at a brisk pace. In this regard, carbon based zero dimensional nanomaterials have attracted vast attention due to their rich optical properties, abundance of raw materials, minimal environmental hazardousness, good solubility, and ease of surface modification. However, efforts focused towards the synthesis of chiral carbon nanodots exhibiting optical activity both in their ground and excited states are rather scarce. Herein, we report a facile synthetic approach for the preparation of three sets of intrinsically chiral carbon nanodots that exhibit intense circularly polarized luminescence. Synthesis under optimized conditions using l- and d-isomers of the chiral precursors led to the formation of carbon nanodots that displayed mirror image circular dichroism and circularly polarized luminescence signals revealing their ground and excited state chirality. The experimental results are supportive of the reported core-shell model comprising an achiral carbon core that is enclosed within an amorphous shell contributing to the chiral luminescence. The luminescence anisotropy and wavelength could be tuned by varying the experimental conditions such as temperature and pH. The chiral emissive properties of the nanoparticles could be demonstrated in free-standing polymeric films revealing their potential to be used as chiral light emitting agents in optical devices, data storage and security tags. Being the first observation of intrinsic circularly polarized luminescence from a range of carbon nanodots, both in the solution and solid state, we envisage that the work will open new avenues for the investigation of excited stated chirality at the nanoscale.

Laser immunotherapy with gold nanorods causes selective killing of tumour cells.

Therapeutic approaches that exploit nanoparticles to deliver drugs selectively to cancer cells are currently considered one of the most promising avenues in the area of cancer therapeutics. Recently, gold nanorods (AuNRs) have shown promising biological applications due to their unique electronic and optical properties. In this paper, we have demonstrated the anti-cancer potential of gold nanorods with low power laser light. Gold nanorods (AuNRs), surface modified with poly (styrene sulfonate) PSS and functionalized with epidermal growth factor receptor antibody conjugated with gold nanorods (anti-EGFR-AuNRs) were successfully synthesised and characterized by UV-Visible-NIR spectrophotometry and High Resolution Transmission Electron Microscopy (HR-TEM). Inductively Coupled Plasmon Atomic Emission Spectrometry (ICP-AES) and Immunofluorescence studies confirmed the efficient uptake of these functionalized gold nanorods by human squamous carcinoma cells, A431. The in vitro photothermal therapy was conducted in four groups - control, laser alone, unconjugated AuNRs with laser and anti-EGFR conjugated AuNRs with laser. Phase contrast images have revealed cell morphology changes and cell death after the laser irradiation. In order to determine whether the cell death occur due to apoptosis or necrosis, we have evaluated the biochemical parameters such as lactate dehydrogenase release, reactive oxygen species level, mitochondrial membrane potential and caspase-3 activity. Flow cytometry analysis have shown the cell cycle changes after laser irradiation with antibody conjugated gold nanorods. Thus the results of our experiments confirmed that immunolabeled gold nanorods can selectively destruct the cancer cells and induce its apoptosis through ROS mediated mitochondrial pathway under low power laser exposure.

Selective photothermal efficiency of citrate capped gold nanoparticles for destruction of cancer cells.

Gold nanoparticles are recently having much attention because of their increased applications in biomedical fields. In this paper, we demonstrated the photothermal efficacy of citrate capped gold nanoparticles (AuNPs) for the destruction of A431 cancer cells. Citrate capped AuNPs were synthesized successfully and characterized by UV-visible-NIR spectrophotometry and High Resolution Transmission Electron Microscopy (HR-TEM). Further, AuNPs were conjugated with epidermal growth factor receptor antibody (anti-EGFR) and applied for the selective photothermal therapy (PTT) of human epithelial cancer cells, A431. PTT experiments were conducted in four groups, Group I--control cells, Group II--cells treated with laser light alone, Group III--cells treated with unconjugated AuNP and further laser irradiation and Group IV--anti-EGFR conjugated AuNP treated cells irradiated by laser light. After laser irradiation, cell morphology changes that were examined using phase contrast microscopy along with the relevant biochemical parameters like lactate dehydrogenase activity, reactive oxygen species generation and caspase-3 activity were studied for all the groups to determine whether cell death occurs due to necrosis or apoptosis. From these results we concluded that, these immunotargeted nanoparticles could selectively induce cell death via ROS mediated apoptosis when cells were exposed to a low power laser light.