Ali M. Jawaid

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.

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.

Shape-controlled colloidal synthesis of rock-salt lead selenide nanocrystals.

Developing simple synthetic methods to control the size and morphology of nanocrystals is an active area of research as these parameters control the materials electronic and optical properties. For a semiconductor with a symmetrical crystal structure such as lead selenide, anisotropic colloidal growth has been previously accomplished via the use of templates, seeds, or by block assembly of smaller, symmetrical subunits. Here, we present a simple method to create monodisperse lead selenide nanorods and multipods at low temperatures. The size distribution and the observed morphologies are consistent with a continuous, anisotropic growth of material. The syntheses of these anisotropic shapes are due to the nature of the nuclei that form upon injection of precursors into partially oxidized alkene solvents that may contain lactone and carbonate-functional derivatives.

Redox Exfoliation of Layered Transition Metal Dichalcogenides

Transition metal dichalcogenides (TMDs) have attracted considerable attention in a diverse array of applications due to the breadth of possible property suites relative to other low-dimensional nanomaterials (e.g., graphene, aluminosilicates). Here, we demonstrate an alternative methodology for the exfoliation of bulk crystallites of group V-VII layered TMDs under quiescent, benchtop conditions using mild redox chemistry. Anionic polyoxometalate species generated from edge sites adsorb to the TMD surface and create Coulombic repulsion that drives layer separation without the use of shear forces. This method is generalizable (MS2, MSe2, and MTe2) and effective in preparing high-concentration (>1 mg/mL) dispersions with narrow layer thickness distributions more rapidly and with safer reagents than alternative solution-based approaches. Finally, exfoliation of these TMDs is demonstrated in a range of solvent systems that were previously inaccessible due to large surface energy differences. These characteristics could be beneficial in the preparation of high-quality films and monoliths.

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%.

Highly Concentrated Seed-Mediated Synthesis of Monodispersed Gold Nanorods

The extremely large optical extinction coefficient of gold nanorods (Au-NRs) enables their use in a diverse array of technologies, rnging from plasmonic imaging, therapeutics and sensors, to large area coatings, filters, and optical attenuators. Development of the latter technologies has been hindered by the lack of cost-effective, large volume production. This is due in part to the low reactant concentration required for symmetry breaking in conventional seed-mediated synthesis. Direct scale up of laboratory procedures has limited viability because of excessive solvent volume, exhaustive postsynthesis purification processes, and the generation of large amounts of waste (e.g., hexadecyltrimethylammonium bromide(CTAB)). Following recent insights into the growth mechanism of Au-NRs and the role of seed development, we modify the classic seed-mediated synthesis via temporal control of seed and reactant concentration to demonstrate production of Au-NRs at more than 100-times the conventional concentration, while maintaining independent control and narrow distribution of nanoparticle dimensions, aspect ratio, and volume. Thus, gram scale synthesis of Au-NRs with prescribed aspect ratio and volume is feasible in a 100 mL reactor with 1/100th of organic waste relative to conventional approaches. Such scale-up techniques are crucial to cost-effectively meet the increased demand for large quantities of Au-NRs in emerging applications.

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.