Synthesis, optical properties and theoretical modelling of discrete emitting states in doped silicon nanocrystals for bioimaging.

The creation of multiple emission pathways in quantum dots (QDs) is an exciting prospect with fundamental interest and optoelectronic potential. For the first time, we report multiple emission pathways in semiconductor nanocrystals (NCs) where the number of emission pathways desired is controlled by the number of dopant atoms per quantum dot. The origin of additional emission pathways is explained by interactions between dopant states and NC energy levels. Density functional theory (DFT) calculations of undoped 2.3 nm silicon (Si NCs) and the same NCs doped with 2 interstitial Cu atoms show good agreement to experiment. Such calculations provide valuable data to explain the changes in optical transitions due to the Cu dopant in terms of transition energies, quantum yield and dopant position as a function of dopants per NC. Changes in the optical properties of Si NCs induced by dopant concentration include extended excitation range and enhanced absorption coefficients, emission redshifts of up to 60 nm, and a two-fold increase in quantum yields up to 22%. The optical properties of doped NCs lead to significant bioimaging improvements illustrated by in vitro cell imaging, including redshifted excitation wavelengths away from natural autofluorescence and enhanced fluorescent signals.

Size and shape evolution of highly magnetic iron nanoparticles from successive growth reactions.

We present a synthetic protocol for the solution-phase synthesis of monocrystalline, metallic iron nanoparticles based on seed-mediated growth, showing near-single nanometre control over particle size. A shape evolution to cubic nanoparticles is also observed with increasing size. Magnetic properties were measured after surface oxidation, showing the potential of our protocol to tune the magnetism of iron nanoparticles for applications requiring superparamagnetic or ferromagnetic nanoparticles.

Role of Surface Capping Molecule Polarity on the Optical Properties of Solution Synthesized Germanium Nanocrystals.

The role surface capping molecules play in dictating the optical properties of semiconductor nanocrystals (NCs) is becoming increasingly evident. In this paper the role of surface capping molecule polarity on the optical properties of germanium NCs (Ge NCs) is explored. Capping molecules are split into two groups: nonpolar and polar. The NCs are fully characterized structurally and optically to establish the link between observed optical properties and surface capping molecules. Ge NC optical properties altered by surface capping molecule polarity include emission maximum, emission lifetime, quantum yield, and Stokes shift. For Ge NCs, this work also allows rational tuning of their optical properties through changes to surface capping molecule polarity, leading to improvements in emerging Ge based bioimaging and optoelectronic devices.

Synthesis and catalytic properties of highly branched palladium nanostructures using seeded growth.

In order to develop nanocatalysts with enhanced catalytic performance, it is important to be able to synthesize nanocrystals enclosed by high-index surface facets, due to their high density of low coordinated atoms at step, ledge and kink sites. Here, we report a facile seed-mediated route to the synthesis of highly branched Pd nanostructures with a combination of {113}, {115} and {220} high-index surface planes. The size of these nanostructures is readily controlled by a simple manipulation of the seed concentration. The selective use of oleylamine and oleic acid was also found to be critical to the synthesis of these structures, with Pd icosahedra enclosed by low-index {111} facets being produced when hexadecylamine was employed as capping ligand. The structure-property relationship of these nanostructures as catalysts in Suzuki-cross coupling reactions was then investigated and compared, with the high-index faceted branched Pd nanostructures found to be the most effective catalysts.

Effects of aging and dietary restriction on DNA polymerase expression in mice.

DNA polymerase alpha was isolated from livers of 6-month-, 16-month-, or 26-month-old mice fed ad libitum, or calorically restricted. The enzymes differed in chromatographic characteristics, binding affinity for DNA, and activity, with both total activity and specific activity of DNA polymerase alpha decreasing as a function of age. A positive correlation was observed between polymerase alpha specific activity and the affinity of enzyme binding to activated DNA template-primer. The age-associated decline in enzyme activity was modified by dietary restriction, with measurably higher activity seen for polymerases from dietary restricted animals compared with ad libitum animals of all ages. The data suggest that dietary restriction could act to delay the age-associated decrease in cellular capacity for DNA synthesis, which may play a significant role in prolonging the onset of age-related diseases in which decreased DNA synthesis is a potential component.

Effect of dietary restriction on the fidelity of DNA polymerases in aging mice.

DNA polymerases purified from hepatic tissues of C57BL/6 mice showed an age-related decrease in both specific activity and fidelity of the various enzyme forms. Polymerases from dietary restricted mice exhibited less of a decline in specific activity and copied synthetic DNA templates with relatively higher fidelity than did enzymes from animals fed ad libitum. Polymerases treated with inositol-1,4-bisphosphate [I(1,4)P2] showed varying levels of increased activity, with fidelity increases up to 3-fold. These data indicate that aging is associated with decreases in both specific activity and fidelity of DNA polymerases isolated from a nondividing tissue, and that dietary restriction impedes the age-related decline in both specific activity and fidelity of these polymerases. The data further indicate that DNA polymerases may interact with phosphoinositide hydrolysis products resulting in increased specific activity and fidelity of the enzymes. Phosphoinositide interactions with polymerases could constitute an important mechanism moderating the age-related decrease in function and accuracy of DNA polymerases.

Interaction of phosphatidylinositol-4-monophosphate with a low activity form of DNA polymerase alpha: a potential mechanism for enzyme activation.

1. DNA polymerase alpha isolated from Norman murine myxosarcoma exhibited two isozyme forms, one with low specific activity and low DNA binding affinity (A1), and one with high specific activity and high DNA binding affinity (A2). 2. DNA polymerase alpha A1, but not A2, showed a significant increase in specific activity after treatment with phosphatidylinositol, ATP and phosphatidylinositol kinase, or with phosphatidylinositol-4-monophosphate. 3. Treatment of DNA polymerase alpha A1 with the phospholipase C hydrolysis product of phosphatidylinositol-4-monophosphate, inositol-1,4-bisphosphate, was sufficient to effect the transient increase in activity of polymerase A1 to a form not chromatographically distinguishable from isozyme form A2.