Quantum Dots for Improved Single-Molecule Localization Microscopy.

Colloidal semiconductor quantum dots (QDs) have long established their versatility and utility for the visualization of biological interactions. On the single-particle level, QDs have demonstrated superior photophysical properties compared to organic dye molecules or fluorescent proteins, but it remains an open question as to which of these fundamental characteristics are most significant with respect to the performance of QDs for imaging beyond the diffraction limit. Here, we demonstrate significant enhancement in achievable localization precision in QD-labeled neurons compared to neurons labeled with an organic fluorophore. Additionally, we identify key photophysical parameters of QDs responsible for this enhancement and compare these parameters to reported values for commonly used fluorophores for super-resolution imaging.

Light-driven hydrogen production with CdSe quantum dots and a cobalt glutathione catalyst.

A photocatalytic hydrogen (H2) production system is reported using glutathione (GSH)-capped CdSe QDs with a cobalt precatalyst, yielding 130 000 mol H2 per mol cobalt over 48 hours. Analysis of the reaction mixtures after catalysis indicates that the active catalyst is a labile complex of cobalt and GSH formed in situ.

Semiconductor nanocrystal photocatalysis for the production of solar fuels.

Colloidal semiconducting nanocrystals (NCs) are powerful elements of a photocatalytic system useful for enabling a variety of chemical transformations owing to their strong light-absorbing properties and high degree of size-, shape-, and composition-tunability. Key to their utility is our understanding of the photoinduced charge transfer processes required for these photochemical transformations. This Perspective will focus on the implementation of semiconductor NCs for photochemical fuel formation. Three general system designs for photocatalytic proton reduction using semiconductor NCs will be reviewed: metal-semiconductor heterostructures, NC photosensitizers with molecular catalysts, and hydrogenase-based systems. Other relevant reactions toward solar fuel targets, such as CO2 and N2 reductions with NCs, will also be highlighted. Illustrating the versatile roles that NCs can play in light-driven chemical reactions, advances made toward NC-catalyzed organic transformations will be discussed. Finally, we will share a few concluding thoughts and perspectives on the future of the field, with a focus on goals toward improving and implementing NC-based technologies for solar fuel development.

Size dependence of photocatalytic hydrogen generation for CdTe quantum dots.

CdTe quantum dots (QDs) are attractive photosensitizers for photocatalytic proton reduction due to their broad absorbance profile that can extend from the ultraviolet to near-infrared regions, providing access to a larger portion of the solar spectrum than possible with analogous CdSe and CdS QD photosensitizers. Here, the photocatalytic hydrogen (H2) generation from various sizes of dihydrolipoic acid (DHLA)-capped CdTe QDs, ranging from 2.5 to 7.5 nm in diameter, and a molecular Ni-DHLA catalyst in aqueous solutions was evaluated, and an unusual size-dependent photocatalytic activity with CdTe QDs was observed. Under optimized conditions, using 3.4 nm CdTe-DHLA and a 1:20 ratio of QD/Ni-DHLA catalyst, as many as 38 000 turnover numbers (mol H2 per mol QD) were achieved. However, below this critical size, the H2 production efficiency decreased; this behavior is attributed to the rapid oxidation of the QD surface, resulting in detrimental surface trap states. These results are consistent with ultrafast transient absorption spectroscopic measurements, which suggest the presence of extremely fast charge-trapping processes in the oxidized CdTe-DHLA QDs. While fast electron transfer from CdTe-DHLA QDs is observed in the presence of the Ni-DHLA catalyst, the charge trapping processes occur on a competitive time scale, thus lowering the efficiency of the CdTe/Ni-DHLA H2 production system. Understanding rapid charge trapping in CdTe QDs may help suggest potential improvements for the overall CdTe photocatalytic system.

Semiconductor quantum dot-sensitized rainbow photocathode for effective photoelectrochemical hydrogen generation.

The present study reports the fabrication of CdSe quantum dot (QD)-sensitized photocathodes on NiO-coated indium tin oxide (ITO) electrodes and their H2-generating ability upon light irradiation. A well-established spin-coating method was used to deposit CdSe QD stock solution onto the surface of NiO/ITO electrodes, thereby leading to the construction of various CdSe QD-sensitized photocathodes. The present report includes the construction of rainbow photocathodes by spin-coating different-sized QDs in a sequentially layered manner, thereby creating an energetically favorable gradient for charge separation. The resulting rainbow photocathodes with forward energetic gradient for charge separation and subsequent electron transfer to a solution-based hydrogen-evolving catalyst (HEC) exhibit good light-harvesting ability and enhanced photoresponses compared with the reverse rainbow photocathodes under white LED light illumination. Under minimally optimized conditions, a photocurrent density of as high as 115 µA⋅cm-2 and a Faradaic efficiency of 99.5% are achieved, which is among the most effective QD-based photocathode water-splitting systems.

Temperature-dependent optical properties of lead selenide quantum dot polymer nanocomposites.

The optical properties of PbSe quantum dots (QDs) in AB9093 epoxy nanocomposite are examined with respect to temperature over a range of 0°C-80°C, a useful working range for many QD-based sensors and devices, and results are compared to QDs in toluene solution. A complete characterization of QD optical properties is provided as a function of temperature, including the absorption spectrum, first excitonic (1-s) absorption peak intensity and wavelength, fluorescence intensity, and peak wavelength. QD optical properties in toluene were found to be more sensitive to temperature as compared to those in AB9093. Interestingly, 1-s and fluorescence peak wavelength variation with temperature are reversed in AB9093 as compared to those in toluene solution. Results for the fluorescence properties of Lumogen F Red 305 dye in toluene are presented for comparison. The dye was found to have similar sensitivity to temperature to that of the QDs in terms of fluorescence peak wavelength shift, but the fluorescence peak intensity was far less variant. These results can be used to build a temperature sensor or as a guide to building other types of QD-based devices to be more robust against changes in ambient temperature.