Research related to the development and application of luminescent nanoparticles (LNPs) for chemical and biological analysis and imaging is flourishing. Novel materials and new applications continue to be reported after two decades of research. This review provides a comprehensive and heuristic overview of this field. It is targeted to both newcomers and experts who are interested in a critical assessment of LNP materials, their properties, strengths and weaknesses, and prospective applications. Numerous LNP materials are cataloged by fundamental descriptions of their chemical identities and physical morphology, quantitative photoluminescence (PL) properties, PL mechanisms, and surface chemistry. These materials include various semiconductor quantum dots, carbon nanotubes, graphene derivatives, carbon dots, nanodiamonds, luminescent metal nanoclusters, lanthanidedoped upconversion nanoparticles and downshifting nanoparticles, triplet−triplet annihilation nanoparticles, persistent-luminescence nanoparticles, conjugated polymer nanoparticles and semiconducting polymer dots, multi-nanoparticle assemblies, and doped and labeled nanoparticles, including but not limited to those based on polymers and silica. As an exercise in the critical assessment of LNP properties, these materials are ranked by several application-related functional criteria. Additional sections highlight recent examples of advances in chemical and biological analysis, point-of-care diagnostics, and cellular, tissue, and in vivo imaging and theranostics. These examples are drawn from the recent literature and organized by both LNP material and the particular properties that are leveraged to an advantage. Finally, a perspective on what comes next for the field is offered.
Semiconducting polymer nanoparticles (Pdots) are a promising fluorescent probe for a wide variety of bioanalytical applications, including as donors in energy transfer (ET)-based sensing and photodynamic therapy. Although numerous Pdot-ET systems have been developed, detailed characterization of the ET mechanisms in these systems has been comparatively limited. Here, we studied the mechanism of ET between Pdot donors based on poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) and a variety of cyanine and rhodamine dye acceptors using both steady-state and time-resolved spectroscopies. The dyes were either hydrophobic and nonspecifically associated with the Pdot core, or hydrophilic and specifically conjugated to the Pdot surface. Our data suggest that Förster resonance energy transfer (FRET) was the most probable and dominant mechanism of ET. There were no clear indications of photoinduced electron transfer (PET) and no need to distinguish Dexter ET from FRET, but there was an apparent decrease in the quantum yield of the acceptor dyes upon association with the Pdots. We also address how the physical characteristics of the Pdot system complicated and limited detailed photophysical study and models, and, in general, render simple FRET models both quantitatively and qualitatively inadequate. The results of our study contribute to a more complete understanding of the ET processes occurring in Pdot-acceptor systems, support the development of both new and improved applications based on Pdots and ET, and inform directions for further fundamental study.
The prerequisites for maximizing the advantageous optical properties of colloidal semiconductor quantum dots (QDs) in biological applications are effective surface functionalization and bioconjugation strategies. Functionalization with dextran has been highly successful with some nanoparticle materials, but has had very limited application with QDs. Here, we report the preparation, characterization, and proof-of-concept applications of dextranfunctionalized QDs. Multiple approaches to dextran ligands were evaluated, including performance with respect to colloidal stability across a range of pH, nonspecific binding with proteins and cells, and microinjection into cells and viability assays. Multiple bioconjugation strategies were demonstrated and applied, including covalent coupling to develop a simple pH sensor, binding of polyhistidinetagged peptides to the QD for energy transfer-based proteolytic activity assays, and binding with tetrameric antibody complexes (TACs) to enable a sandwich immunoassay and cell immunolabeling and imaging. Our results show that dextran ligands are highly promising for the functionalization of QDs, and that the design of the ligands is tailorable to help optimally meet the requirements of applications.
We present the first systematic study of 2,2'-bipyridine complexes of E(ii) cationic acceptors (E = Ge, Sn). The complexes were comprehensively characterized by spectroscopic and crystallographic methods to yield complexes of ECl and E. Computational DFT methods were also employed to survey the bonding in the cations, along with an examination of their molecular orbitals (MOs).
Concentric Förster resonance energy transfer (cFRET) is an emerging concept for single-vector multiplexed bioanalysis and imaging. It features a network of competitive and sequential energy transfer pathways, which, to date, has been assembled with a central semiconductor quantum dot (QD) and biomolecular linkers to multiple copies of multiple types of concentrically-arranged fluorescent dyes. In this review, we provide a first-hand account of the concept and development of cFRET, starting from its place in the broader context of FRET probes and assemblies. Topics of discussion include materials for cFRET, with a focus on the enabling properties of QDs and the ideal properties of nominal acceptor dyes; characterization and analysis of cFRET configurations via photoluminescence intensity, emission ratio, lifetime, and photobleaching measurements; semi-empirical modeling to determine the rates and efficiencies of competitive and sequential FRET pathways from overall quenching efficiencies; and archetypical examples of cFRET configurations and their application in bioanalysis and imaging. Most of the latter examples demonstrate multiplexed detection of protease activity or nucleic acid targets. Examples of atypical and cFRET-like configurations are also discussed, including those that utilize time-gated FRET relays and charge-transfer quenching. We conclude with a perspective on challenges and directions for future research with cFRET. Although still emerging as a method, many exciting opportunities in bioanalysis, imaging, and beyond are envisioned for cFRET.
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