Luminescent nanomaterials such as semiconductor nanocrystals (NCs) and quantum dots (QDs) attract much attention to optical detectors, LEDs, photovoltaics, displays, biosensing, and bioimaging. These materials include metal chalcogenide QDs and metal halide perovskite NCs. Since the introduction of cadmium chalcogenide QDs to biolabeling and bioimaging, various metal nanoparticles (NPs), atomically precise metal nanoclusters, carbon QDs, graphene QDs, silicon QDs, and other chalcogenide QDs have been infiltrating the nano-bio interface as imaging and therapeutic agents. Nanobioconjugates prepared from luminescent QDs form a new class of imaging probes for cellular and in vivo imaging with single-molecule, super-resolution, and 3D resolutions. Surface modified and bioconjugated core-only and core-shell QDs of metal chalcogenides (MX; M = Cd/Pb/Hg/Ag, and X = S/Se/Te,), binary metal chalcogenides (MInX2; M = Cu/Ag, and X = S/Se/Te), indium compounds (InAs and InP), metal NPs (Ag, Au, and Pt), pure or mixed precision nanoclusters (Ag, Au, Pt), carbon nanomaterials (graphene QDs, graphene nanosheets, carbon NPs, and nanodiamond), silica NPs, silicon QDs, etc. have become prevalent in biosensing, bioimaging, and phototherapy. While heavy metal-based QDs are limited to in vitro bioanalysis or clinical testing due to their potential metal ion-induced toxicity, carbon (nanodiamond and graphene) and silicon QDs, gold and silica nanoparticles, and metal nanoclusters continue their in vivo voyage towards clinical imaging and therapeutic applications. This review summarizes the synthesis, chemical modifications, optical properties, and bioimaging applications of semiconductor QDs with particular references to metal chalcogenide QDs and bimetallic chalcogenide QDs. Also, this review highlights the toxicity and pharmacokinetics of QD bioconjugates.

Atomically precise nanoclusters (NCs) have recently emerged as ideal building blocks for constructing self-assembled multifunctional superstructures. The existing structures are based on various non-covalent interactions of the ligands on the NC surface, resulting in inter-NC interactions. Despite recent demonstrations on light-induced reversible self-assembly, long-range reversible self-assembly based on dynamic covalent chemistry on the NC surface has yet to be investigated. Here, it is shown that Au25 NCs containing thiolated umbelliferone (7-hydroxycoumarin) ligands allow [2+2] photocycloaddition reaction-induced self-assembly into colloidal-level toroids. The toroids upon further irradiation undergo inter-toroidal reaction resulting in macroscopic supertoroidal honey-comb frameworks. Systematic investigation using electron microscopy, atomic force microscopy (AFM), and electron tomography (ET) suggest that the NCs initially form spherical aggregates. The spherical structures further undergo fusion resulting in toroid formation. Finally, the toroids fuse into macroscopic honeycomb frameworks. As a proof-of-concept, a cross-photocycloaddition reaction between coumarin-tethered NCs and an anticancer drug (5-fluorouracil) is demonstrated as a model photo-controlled drug release system. The model system allows systematic loading and unloading of the drug during the assembly and disassembly under two different wavelengths. The results suggest that the dynamic covalent chemistry on the NC surface offers a facile route for hierarchical multifunctional frameworks and photocontrolled drug release.

Atomically precise noble metal nanoclusters (precision nanoclusters) have evolved into an important class of materials in the field of nanoscience over the past two decades. Nanoclusters are made up of a few to hundreds of atoms stabilized with a certain number of surface ligands. The origin of these materials has helped bridge the missing gap between the molecules and nanoparticles. Unlike plasmonic nanoparticles, nanoclusters exhibit distinct absorption peaks in the UV-Vis-NIR region due to their molecular-like electronic transitions resulting from the quantum confinement. Advanced mass spectroscopy and single-crystal X-ray diffraction investigations have helped solve the molecular composition (Mx(L)y) of many nanoclusters. Among these, nanoclusters derived from coinage metals (gold, silver, and copper) have received substantial interest recently because of their easy synthesis protocols, established purification techniques, ultrasmall size (<2 nm), exceptional photo/chemical stability, bright photoluminescence, and low toxicity. Though nanoclusters have been used for a broad spectrum of applications, this chapter covers their uses in molecular/metal ion sensing, device fabrication, green energy harvesting, photocatalysis, and the biomedical field.

We demonstrate the synthesis and photon-induced reversible self-assembly of azobenzene-alkyl monothiol(C3-AMT)-tethered Au25 NCs.

Despite tremendous progress in the field of fluorescence-based anticounterfeiting, the advanced anticounter-feiting techniques are still posing challenges all over the world due to their cost and reliability. Recently, light-emitting atomically precise nanoclusters have emerged as attractive building blocks because of their well-defined structure, function, and stable photoluminescence. Herein, we report the room temperature fabrication of a stable, flexible, nontoxic, and low-cost precision nanocluster-based luminescent ink for the stencil printing of an optically unclonable security label. Nanocluster-based printing ink shows brilliant photoluminescence owing to its extended C− H···π/π···π interactions. Spectroscopic and microscopic investigations show that intercalated nanoclusters in the printed security labels are highly stable as their optical features and molecular compositions are unaffected. The exceptional mechanical, thermal, photo, and aqueous stabilities of the printed security labels endorse to demonstrate the printing and smartphone-based electronic reading of the quick response code on a currency. Finally, confidential information protection and decryption under a precise window of light have been achieved by adopting the optical contrast illusion. The overall cost of the security label is found to be approximately 0.013 USD per stamp.