Suitable labels are at the core of Luminescence and fluorescence imaging and sensing. One of the most exciting, yet also controversial, advances in label technology is the emerging development of quantum dots (QDs)--inorganic nanocrystals with unique optical and chemical properties but complicated surface chemistry--as in vitro and in vivo fluorophores. Here we compare and evaluate the differences in physicochemical properties of common fluorescent labels, focusing on traditional organic dyes and QDs. Our aim is to provide a better understanding of the advantages and limitations of both classes of chromophores, to facilitate label choice and to address future challenges in the rational design and manipulation of QD labels.

/pdf/quantum-dots-versus-organic-dyes-as-fluorescent-labels-50cbzj94q6.pdf

Quantum dots versus organic dyes as fluorescent labels

Inorganic colloidal nanoparticles are very small, nanoscale objects with inorganic cores that are dispersed in a solvent. Depending on the material they consist of, nanoparticles can possess a number of different properties such as high electron density and strong optical absorption (e.g. metal particles, in particular Au), photoluminescence in the form of fluorescence (semiconductor quantum dots, e.g. CdSe or CdTe) or phosphorescence (doped oxide materials, e.g. Y(2)O(3)), or magnetic moment (e.g. iron oxide or cobalt nanoparticles). Prerequisite for every possible application is the proper surface functionalization of such nanoparticles, which determines their interaction with the environment. These interactions ultimately affect the colloidal stability of the particles, and may yield to a controlled assembly or to the delivery of nanoparticles to a target, e.g. by appropriate functional molecules on the particle surface. This work aims to review different strategies of surface modification and functionalization of inorganic colloidal nanoparticles with a special focus on the material systems gold and semiconductor nanoparticles, such as CdSe/ZnS. However, the discussed strategies are often of general nature and apply in the same way to nanoparticles of other materials.

https://faculty.washington.edu/mzhang/mse599/Surface-modification.full.pdf

Surface modification, functionalization and bioconjugation of colloidal inorganic nanoparticles

We demonstrate that metal carboxylate complexes (L–M(O2CR)2, R = oleyl, tetradecyl, M = Cd, Pb) are readily displaced from carboxylate-terminated ME nanocrystals (ME = CdSe, CdS, PbSe, PbS) by various Lewis bases (L = tri-n-butylamine, tetrahydrofuran, tetradecanol, N,N-dimethyl-n-butylamine, tri-n-butylphosphine, N,N,N′,N′-tetramethylbutylene-1,4-diamine, pyridine, N,N,N′,N′-tetramethylethylene-1,2-diamine, n-octylamine). The relative displacement potency is measured by 1H NMR spectroscopy and depends most strongly on geometric factors such as sterics and chelation, although also on the hard/soft match with the cadmium ion. The results suggest that ligands displace L–M(O2CR)2 by cooperatively complexing the displaced metal ion as well as the nanocrystal. Removal of up to 90% of surface-bound Cd(O2CR)2 from CdSe and CdS nanocrystals decreases the Cd/Se ratio from 1.1 ± 0.06 to 1.0 ± 0.05, broadens the 1Se–2S3/2h absorption, and decreases the photoluminescence quantum yield (PLQY) from 10% to <1% (CdSe) an...

/pdf/ligand-exchange-and-the-stoichiometry-of-metal-chalcogenide-mvgek5d5ry.pdf

Ligand exchange and the stoichiometry of metal chalcogenide nanocrystals: spectroscopic observation of facile metal-carboxylate displacement and binding.

Through the use of photoelectron spectroscopy in air (PESA), we investigate the size-dependent valence and conduction band-edge energies of CdSe, CdTe, PbS, and PbSe semiconductor quantum dots (QDs). The results are compared to those of previous studies, based on differing experimental methods, and to theoretical calculations based on k·p theory and state-of-the-art atomistic semiempirical pseudopotential modeling. To accurately map out the energy level landscapes of QDs as a function of size, the QDs must be passivated by comparable surface chemistries. This is highlighted by studying the effect of surface chemistry on the valence band-edge energy in an ensemble of 4.7 nm CdSe QDs. An energy level shift as large as 0.35 eV is observed for this system through modification of surface chemistry alone. This shift is significantly larger than the size-dependent valence band-edge shift that is observed when comparable surface chemistries are used.

Size-dependent valence and conduction band-edge energies of semiconductor nanocrystals.

Despite the increasing use of semiconductor nanocrystals (quantum dots, QDs) with unique size-controlled optical and chemical properties in (bio)analytical detection, biosensing and fluorescence imaging and the obvious relevance of reliable values of fluorescence quantum yields for these applications, evaluated procedures for the determination of the fluorescence quantum yields (Φf) of these materials are still missing. This limits the value of literature data of QDs in comparison to common organic dyes and hampers the comparability of the performance of QDs from different sources or manufacturers. This encouraged us to investigate achievable uncertainties for the determination of Φf values of these chromophores and to illustrate common pitfalls exemplarily for differently sized water-soluble CdTe QDs. Special attention is dedicated to the colloidal nature and complicated surface chemistry of QDs thereby deriving procedures to minimize uncertainties related to these features.

Determination of the Fluorescence Quantum Yield of Quantum Dots: Suitable Procedures and Achievable Uncertainties

With CdSe nanocrystals stabilized with very weak ligands (pyridine) as the starting materials, NMR techniques were applied to distinguish the bonded and free alkylamine ligands in an equilibrated adsorption/desorption system for the CdSe−amine nanocrystal−ligand pair. NMR and photoluminescence (PL) measurements were further correlated to identify the linear relationship between PL intensity and the surface ligand coverage of the amine-coated CdSe nanocrystals. For 3.5 nm CdSe nanocrystals and octylamine ligands, the chemical equilibrium constant (K) of the CdSe−amine nanocrystal−ligand adsorption/desorption process was found to be around 50−100, and the corresponding ΔrGo was calculated as 9.8−11.5 kJ/mol. With a proposed mathematic method, the corresponding chemical kinetic constants for the desorption (kd) and adsorption (ka) processes were measured to be 0.01 s-1 and 0.5 L mol-1 s-1, respectively. K, kd, and ka obtained here are generally 2−4 magnitudes different from those estimated in literature. Ana...

Danis Copenhaver

Papers

Ligand Bonding and Dynamics on Colloidal Nanocrystals at Room Temperature: The Case of Alkylamines on CdSe Nanocrystals