Ratiometric QD-FRET Sensing of Aqueous H2S in Vitro.

We report a platform for the ratiometric fluorescent sensing of endogenously generated gaseous transmitter H2S in its aqueous form (bisulfide or hydrogen sulfide anion) based on the alteration of Förster resonance energy transfer from an emissive semiconductor quantum dot (QD) donor to a dithiol-linked organic dye acceptor. The disulfide bridge between the two chromophores is cleaved upon exposure to bisulfide, resulting in termination of FRET as the dye diffuses away from the QD. This results in enhanced QD emission and dye quenching. The resulting ratiometric response can be correlated quantitatively to the concentration of bisulfide and was found to have a detection limit as low as 1.36 ± 0.03 µM. The potential for use in biological applications was demonstrated by measuring the response of the QD-based FRET sensor microinjected into live HeLa cells upon extracellular exposure to bisulfide. The methodology used here is built upon a highly multifunctional platform that offers numerous advantages, such as low detection limit, enhanced photochemical stability, and sensing ability within a biological milieu.

Monolayer Silane-Coated, Water-Soluble Quantum Dots.

A one-step method to produce ≈12 nm hydrodynamic diameter water-soluble CdSe/ZnS quantum dots (QDs), as well as CdS/ZnS, ZnSe/ZnMnS/ZnS, AgInS2 /ZnS, and CuInS2 /ZnS QDs, by ligand exchange with a near-monolayer of organosilane caps is reported. The method cross-links the surface-bound silane ligands such that the samples are stable on the order of months under ambient conditions. Furthermore, the samples may retain a high quantum yield (60%) over this time. Several methods to functionalize aqueous QD dispersions with proteins and fluorescent dyes have been developed with reaction yields as high as 97%.

QD-Based FRET Probes at a Glance.

The unique optoelectronic properties of quantum dots (QDs) give them significant advantages over traditional organic dyes, not only as fluorescent labels for bioimaging, but also as emissive sensing probes. QD sensors that function via manipulation of fluorescent resonance energy transfer (FRET) are of special interest due to the multiple response mechanisms that may be utilized, which in turn imparts enhanced flexibility in their design. They may also function as ratiometric, or "color-changing" probes. In this review, we describe the fundamentals of FRET and provide examples of QD-FRET sensors as grouped by their response mechanisms such as link cleavage and structural rearrangement. An overview of early works, recent advances, and various models of QD-FRET sensors for the measurement of pH and oxygen, as well as the presence of metal ions and proteins such as enzymes, are also provided.

Selective quantitation of B2Pin2 and B2(OH)4 in active pharmaceutical ingredients by gas chromatography- mass spectrometry.

This paper describes a sensitive and selective method for the simultaneous determination of bispinacolato diboron (B2Pin2) and tetrahydroxy diboron (B2(OH)4) in a small molecule Active Pharmaceutical Ingredient (API) by gas chromatography - mass spectrometry (GC-MS). These reagents are commonly used in the Suzuki-Miyaura coupling reaction and analytical methods are typically required to monitor these reagents at the Threshold of Toxicological Concern (TTC) level since they are Class II impurities based on ICH M7 guideline. In this study, hexylene glycol was added to derivatize B2(OH)4 before direct injection to the GC-MS, and B2Pin2 is analyzed in the same analysis without derivatization. Under the optimal conditions, the limit of detection (LOD) and the limit of quantitation (LOQ) were 65 ng/mL and 130 ng/mL respectively. Average recoveries of the analytes spiked in the drug substance at the 13 ppm (LOQ) and 104 ppm (TTC) levels were in the range of 77.9 %-85.3 % with relative standard deviations (RSDs) of 2.8 %-6.8 %. The linearity for both analytes was established in the range of 0.130-2.080 µg/mL with a correlation coefficient (r) of 0.9998 and the derivatization reaction is very rapid and complete within 15 minutes.

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy.

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Reported here are the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Furthermore, the transient photoluminescence and the kinetics of dopant oxidation reveal the presence of two types of surface-bound ions that create midgap states.

In vitro Detection of Hypoxia using a Ratiometric Quantum Dot-based Oxygen Sensor.

A quantum-dot based ratiometric fluorescent oxygen probe for the detection of hypoxia in live cells is reported. The system is comprised of a water-soluble near-infrared emissive quantum dot conjugated to perylene dye. The response to the oxygen concentration is investigated using enzymatic oxygen scavenging in water, while in vitro studies were performed with HeLa cells incubated under varying O2 levels. In both cases a significant enhancement in dye/QD emission intensity ratio was observed in the deoxygenated environment, demonstrating the possible use of this probe for cancer research.

A toolkit for bioimaging using near-infrared AgInS2/ZnS quantum dots.

Presented are a set of procedures to produce water-soluble AgInS2/ZnS near-infrared emitting quantum dots for use as biological imaging agents. The known difficulty of producing near-infrared core/shell materials is resolved by overcoating the AgInS2 cores at a low temperature using highly reactive precursors. Several methods are explored to impart water solubility of the hydrophobic as-prepared materials. Insofar as achieving aqueous dispersion of quantum dots has only limited biological utility, several methods to further functionalize them are examined. In vivo studies are conducted using these quantum dots to demonstrate the ability to model delivery of nanoparticles to the tumour microenvironment.