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.

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.

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.

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.

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.

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.

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.

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.

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.

Protein fibril assisted chiral assembly of gold nanorods.

Template mediated assembly of plasmonic nanomaterials is a promising approach to induce chirality. Naturally occurring macromolecules can self-assemble to form chiral superstructures, with dimensions extending from nanometer to micrometer length scales. These structures can serve as templates for host plasmonic nanomaterials on their surface through a variety of interactions. The arrangement of nanomaterials on these structures results in a transfer of symmetry from these templates to nanomaterials, which finally generates a chiral response in circular dichroism (CD) spectroscopy. For biosensing and in vitro applications of chiral plasmonics, long-term stability of these templates will be crucial for this approach of chirality induction. Here, we have demonstrated how protein amyloid fibrils can be used as templates to generate a chiroptical response with plasmonic nanomaterials. The temperature and ionic strength of the solution were carefully altered to convert the three-dimensional protein structure into amyloid fibrils. Changes in solution conditions affected the amyloid geometry, long-term stability, and interaction with AuNRs. The modified interactions influenced the orientation of the AuNRs, which affected the intensity of the CD response. The MTT assay indicated that the chiral AuNRs exhibited considerable cell viability, making them ideal for in vivo applications.

A Facile Approach for the Ligand Free Synthesis of Biocompatible Upconversion Nanophosphors.

Upconversion nanophosphors, particles that can absorb low energy radiation and emit high energy light through multi-photon absorption processes, have gained augmented attention in recent years. Due to their admirable optical and chemical properties, these nanoparticles are finding wide range of applications in the field of bioimaging, light emitting devices and security printing. However, for any practical application, it is extremely important that a facile synthetic route is developed that can lead to the generation of nanophosphors exhibiting efficient upconversion luminescence under diverse experimental conditions. Herein, we report a new ligand-free approach for the synthesis of lanthanide-based upconversion nanoparticles by adopting a simple solid-state synthetic route. The reaction conditions such as temperature and time were optimized to obtain nanophosphors exhibiting enhanced upconversion luminescence. The synthesized nanoparticles, due to its ligand-free nature, could be well dispersed in both aqueous and organic media. The nanophosphors retained the upconversion luminescence under varying time, pH and temperature, indicating that the absence of ligand had least effect on their stability. The nanophosphors were found to exhibit good cell viability even under high concentrations, unveiling their potential as bioimaging agents in the biomedical research.

Mandelic acid appended chiral gels as efficient templates for multicolour circularly polarized luminescence.

Mandelic acid is a medicinally important chiral molecule that is widely used as a vital component in antibiotics, antiseptics and cosmetics. While the medicinal properties of mandelic acid are well known, its aggregation and gelation characteristics, which are crucial to finding applications as cosmetics and ointments, are least explored. We have designed and synthesized a pair of mandelic acid derivatives and investigated their aggregation properties in binary solvent mixtures. The compounds undergo self-assembly through various noncovalent interactions, leading to the formation of robust chiral gels. Strong birefringence could be visualised from the individual structures constituting the gel. The large rod-like chiral structures are utilized as efficient templates for the assembly of ultra-small luminescent achiral carbon nanodots. The transfer of optical activity from the chiral host matrix to the fluorescent guest nanoparticles resulted in the generation of circularly polarized luminescence signals from the hybrid nanocomposites. The use of blue, green and red-emitting nanodots led to the fabrication of multicolour chiral light-emitting materials capable of covering the entire visible range. Considering the numerous medicinal benefits offered by mandelic acid and carbon nanodots, the materials constituting the nanocomposites, the distinct dimensions presented in the current work open new avenues for chiral light emitting materials to be used in biomedical research.

In Vivo Evaluation of Multifunctional Gold Nanorods for Boron Neutron Capture and Photothermal Therapies.

The incidence and mortality of cancer demand more innovative approaches and combination therapies to increase treatment efficacy and decrease off-target side effects. We describe a boron-rich nanoparticle composite with potential applications in both boron neutron capture therapy (BNCT) and photothermal therapy (PTT). Our strategy is based on gold nanorods (AuNRs) stabilized with polyethylene glycol and functionalized with the water-soluble complex cobalt bis(dicarbollide) ([3,3'-Co(1,2-C2B9H11)2]-), commonly known as COSAN. Radiolabeling with the positron emitter copper-64 (64Cu) enabled in vivo tracking using positron emission tomography imaging. 64Cu-labeled multifunctionalized AuNRs proved to be radiochemically stable and capable of being accumulated in the tumor after intravenous administration in a mouse xenograft model of gastrointestinal cancer. The resulting multifunctional AuNRs showed high biocompatibility and the capacity to induce local heating under external stimulation and trigger cell death in heterogeneous cancer spheroids as well as the capacity to decrease cell viability under neutron irradiation in cancer cells. These results position our nanoconjugates as suitable candidates for combined BNCT/PTT therapies.

Plasmon-Enhanced Optical Chirality through Hotspot Formation in Surfactant-Directed Self-Assembly of Gold Nanorods.

Plasmonically enhanced optical dichroism has attracted substantial interest for its application in optical sensing, where the interplay between chirality emanating from both molecules and plasmon-supporting structures has been regarded as a critical ingredient. Here, we experimentally demonstrate that suitably self-assembled achiral plasmonic nanostructures produce a high degree of enhancement in the optical dichroism observed from chiral molecules placed in their vicinity. Specifically, we identify a near-field enhancement associated with plasmonic hotpots as the mechanism enabling our observation of visible-NIR circular dichroism emanating from small amounts of chiral molecules. Our structures consist of linear arrays of gold nanorods obtained by introducing chiral anionic surfactants, such as modified bile salts, which lead to selective destabilization of a cetyltrimethylammonium bromide coating layer on Au nanorods, thereby promoting a tip-to-tip oriented assembly. The proposed mechanism of plasmonically-enhanced circular dichroism is supported by deriving a simple, yet general theoretical formalism that confirms the observed results, revealing the role of optical hotspots at the gaps of linear tip-to-tip nanorod assemblies as the origin of enhancement in the dichroism from chiral molecules. Importantly, it is the refractive rather than the absorption-mediated chiral response of the molecules that produces dichroism in the visible-NIR plasmonic regime, far from their UV absorption resonances. The observed self-assembly mechanism suggests that chiral analytes not directly interacting with the nanorod surfaces, but just able to induce tip-to-tip aggregation, can be revealed by a CD signature in the plasmonic region, thereby supporting potential applications in ultrasensitive analysis.

Silver assisted stereo-directed assembly of branched peptide nucleic acids into four-point nanostars.

Branched chiral peptide nucleic acids br(4S/R)-PNA with three arms of PNA-C4 strands were constructed on a central chiral core of 4(R/S)-aminoproline as the branching center. The addition of Ag+ triggered the self-assembly of branched PNAs through the formation of C-Ag+-C metallo base pairing of the three PNA C4 arms leading to non-covalent dendrimers, whose architecture is directed by the C4(R/S)-stereocenter of core 4-aminoproline. The 4S-aminoprolyl core enabled the precise formation of four-pointed nanostars that was not realised with 4R-aminoprolyl or acyclic, achiral aminoethyl glycyl PNA cores. The dendritic assembly of 4 pointed nanostars exhibited net chirality of base stacks in CD spectra, while the base stack assembly from br(4R)-PNA 2 was overall achiral. The results demonstrate that the silver assisted, 4S-aminoproline core stereo selective chiral assembly of branched PNAs manifests into nanostar morphology. The chiral branched PNAs open new vistas in the supramolecular organization of nucleic acids.

Template Assisted Generation of Chiral Luminescence in Organic Fluorophores.

Development of efficient ways of fabricating chiral light emitting materials is an active area of research due to the vast potential offered by these materials in the field of optoelectronic devices, data storage, and asymmetric synthesis. Among the various methods employed, template assisted generation of chiral luminescence is gaining enormous attention due to its simplicity, applicability over a wide range of fluorescent molecules/dyes, and the display of high anisotropic values.

Mechano-responsive circularly polarized luminescence of organic solid-state chiral emitters.

Two difluoro-boron ß-diketonate complexes bearing chiral amido groups have been synthesized. Their mechano-responsive luminescence and chiroptical properties have been investigated in the solid state. Both compounds display a bright blue-green emission and a significant circularly polarized luminescence (CPL) signal in the crystalline state, with |g lum| values as high as 2.2-2.4 × 10-2. A bathochromic shift in emission, together with a decrease of |g lum| values to c.a. 3 × 10-3, is induced upon application of a shearing stress. For the DFB-Hex-amide compound, interestingly, sign inversion of the anisotropy factor g lum is observed under mechanical stimulation ("mechano-CPL effect"), which can be rationalized by a switching between monomer and excimer emission.

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.

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.

Coupling of Elementary Electronic Excitations: Drawing Parallels Between Excitons and Plasmons.

Recent advances in understanding the theoretical and experimental properties of excitons and plasmons have led to several technological breakthroughs. Though emerging from different schools of research, the parallels they possess both in their isolated and assembled forms are indeed interesting. Employing the larger framework of the dipolar coupling model, these aspects are discussed based on the excitonic transitions in chromophores and plasmonic resonances in noble metal nanostructures. The emergence of novel optical properties in linear, parallel, and helical assemblies of chromophores and nanostructures with varying separation distances, orientations, and interaction strengths of interacting dipolar components is discussed. The very high dipolar strengths of plasmonic transitions compared to the excitonic transitions, arising due to the collective nature of the electronic excitations in nanostructures, leads to the emergence of hot spots in plasmonically coupled assemblies. Correlations on the distance dependence of electric field with Raman signal enhancements have paved the way to the development of capillary tube-based plasmonic platforms for the detection of analytes.