Preston T. Snee

Blue semiconductor nanocrystal laser

We demonstrate tunable room-temperature amplified spontaneous emission and lasing from blue-emitting core-shell CdS∕ZnS nanocrystals (NCs) stabilized in a sol-gel derived silica matrix. Variable stripe length measurements show that these NC-silica composites have a modal gain of ∼100cm−1 at room temperature. Coating microspheres with a NC-silica composite film via a facile process resulted in uniform resonators that exhibit room-temperature lasing over long periods of continuous excitation. This work opens up a spectral window for emission tunable, microscale NC-based lasers.

Poly(ethylene glycol) carbodiimide coupling reagents for the biological and chemical functionalization of water-soluble nanoparticles

Many types of metal and semiconductor nanoparticles (NPs) are created via colloidal synthetic methods, which renders the materials hydrophobic. Such NPs are dispersed in water through surface organic cap exchange or by amphiphilic polymer encapsulation; often, water solubility is achieved via the presence of carboxylic acid functionalities on the solubilizing agents. While this renders the material water-soluble, subsequent functionalization of the systems can be very difficult. The most obvious method to derivatize carboxylic acid coated NPs is to conjugate chemical and biological moieties containing amine functionality to the NP surface using the water-soluble activator 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). However, the excess use of this reagent appears to cause complete and permanent precipitation of the NPs. We report here our method on the chemical and biological functionalization of a variety of semiconductor nanoparticle systems using novel carbodiimide reagents. These reagents do not cause precipitation even at high loading levels and can be used to efficiently functionalize carboxylic acid coated NPs.

Multiexcitonic two-state lasing in a CdSe nanocrystal laser

We report simultaneous amplified spontaneous emission from two different multiexcitonic transitions −1Se–1S3∕2 and 1Pe–1P3∕2− of colloidal CdSe nanocrystals (NCs) stabilized in high volume fraction in titania matrices. Two-state lasing from both multiexcitonic transitions is achieved in a surface-emitting distributed feedback CdSe NC laser. Variable stripe length measurements show that the gain from the 1Pe–1P3∕2 transition is approximately twice that of the −1Se–1S3∕2 transition for 4.2nm radius CdSe∕ZnS core-shell NCs.

Water-soluble semiconductor nanocrystals cap exchanged with metalated ligands

We report a novel method for cap exchange of emissive semiconductor nanocrystals (NCs) using thiol functional ligands metalated with zinc. Utilizing this method, the NCs can be several times brighter and much more resistant to precipitation compared to control samples. This method has been applied using a variety of caps such as dihydrolipoic acid and cysteine. Our data suggest that the improved properties of the metalated cap exchanged NCs are due to a ligand metathesis process occurring at the NC surface where the zinc complex reacts with NC surface bound ligands, gently removing them and replacing them with another cap. Overall, the use of metalated ligands helps resolve many long-standing issues concerning the application of small cap exchanged NCs for biological imaging.

A primer on the synthesis, water-solubilization, and functionalization of quantum dots, their use as biological sensing agents, and present status

The use of nanomaterials, specifically fluorescent semiconductor quantum dots (QDs), for biological imaging and sensing has become very topical. Here we present a historical synopsis of research in this field to help elucidate the origins of the most recent advances in QD-based technology. We further aim to educate the novice researcher concerning many important aspects of QD synthesis, water-solubilization, functionalization, and usage in biological imaging and sensing that are generally not discussed in the literature. We will also summarize several recent transformative examples of using quantum dots for in vitro and in vivo studies.

Ratiometric CdSe/ZnS Quantum Dot Protein Sensor

We have created a platform for the ratiometric fluorescent sensing of targeted proteins by conjugating conjoined protein binding agent/organic dye ligands to water-soluble, emissive semiconductor quantum dots (QDs). The QD emission is tuned such that it may serve as an energy transfer donor to the dye acceptor. Upon exposure to the target proteins, these analytes bind to the surfaces of the QDs and change the microenvironments of the QD-bound dyes such that the emissive properties of the dyes are perturbed. The resulting alteration in the QD and dye fluorescence spectra creates a readout that is fully quantitative. The advantage of our methodology is that the detection of proteins is very fast as the platform is fully homogeneous, whereas the heterogeneous ELISA assay involves multiple steps with blocking agents and secondary reporters that ultimately complicate the process. The calculated detection limits for the two QD protein-sensing examples reported here are also competitive with the ubiquitous ELISA assay.

A nanocrystal-based ratiometric pH sensor for natural pH ranges

A ratiometric fluorescent pH sensor based on CdSe/CdZnS nanocrystal quantum dots (NCs) has been designed for biological pH ranges. The construct is formed from the conjugation of a pH dye (SNARF) to NCs coated with a poly(amido amine) (PAMAM) dendrimer. The sensor exhibits a well-resolved ratio response at pH values between 6 and 8 under linear or two-photon excitation, and in the presence of a 4% bovine serum albumin (BSA) solution.

Cluster-Seeded Synthesis of Doped CdSe:Cu4 Quantum Dots

We report here a method for synthesizing CdSe quantum dots (QDs) containing copper such that each QD is doped with four copper ions. The synthesis is a derivative of the cluster-seed method, whereby organometallic clusters act as nucleation centers for quantum dots. The method is tolerant of the chemical identity of the seed; as such, we have doped four copper ions into CdSe QDs using [Na(H2O)3]2[Cu4(SPh)6] as a cluster seed. The controlled doping allows us to monitor the photophysical properties of guest ions with X-ray spectroscopy, specifically XANES and EXAFS at the copper K-edge. These data reveal that copper can capture both electrons and holes from photoexcited CdSe QDs. When the dopant is oxidized, photoluminescence is quenched and the copper ions translocate within the CdSe matrix, which slows the return to an emissive state.

Cluster-Seeded Synthesis of Doped CdSe:Cu[subscript 4] Quantum Dots

We report here a method for synthesizing CdSe quantum dots (QDs) containing copper such that each QD is doped with four copper ions. The synthesis is a derivative of the cluster-seed method, whereby organometallic clusters act as nucleation centers for quantum dots. The method is tolerant of the chemical identity of the seed; as such, we have doped four copper ions into CdSe QDs using [Na(H2O)3]2[Cu4(SPh)6] as a cluster seed. The controlled doping allows us to monitor the photophysical properties of guest ions with X-ray spectroscopy, specifically XANES and EXAFS at the copper K-edge. These data reveal that copper can capture both electrons and holes from photoexcited CdSe QDs. When the dopant is oxidized, photoluminescence is quenched and the copper ions translocate within the CdSe matrix, which slows the return to an emissive state.

Nanoscopic interchain aggregate domain formation in conjugated polymer films studied by third harmonic generation near-field scanning optical microscopy

The electronic structure of conjugated polymer films is of current interest due to the wide range of potential applications for such materials in optoelectronic devices. A central outstanding issue is the significance of interchain electronic species in films of these materials. In this paper, we investigate the nature of interchain species in films of poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) both before and after thermal annealing. Our investigation employs a combination of third harmonic generation (THG) and near-field scanning optical microscopy to measure the wavelength and spatial dependence of the THG efficiency. These chemically selective imaging measurements reveal new, low-energy absorption features in nanometer-scale spatially distinct regions of annealed films that are only infrequently observed prior to annealing. This suggests that the polymer strands in annealed MEH-PPV films pack together closely enough that significant ground-state wave function overlap can occ...