Graduation Year

2010

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemical Engineering

Major Professor

Venkat R. Bhethanabotla, Ph.D.

Co-Major Professor

Rajan Sen, Ph.D.

Committee Member

Randy W. Larsen, Ph.D.

Committee Member

Vinay K. Gupta, Ph.D.

Committee Member

Ryan Toomey, Ph.D.

Keywords

quantum efficiency, oxygen diffusion, Stern-Volmer plot, surface plasmon resonance, alloy nanoparticles, optical properties, dielectric constant

Abstract

The first part of this dissertation deals with the application of a luminescence quenching method to measure diffusion and permeation coefficients of oxygen in polymers. Most luminescence oxygen sensors do not follow linearity of the Stern-Volmer (SV) equation due to heterogeneity of luminophore in the polymer matrix, thus the complexity of data analysis is increased. To circumvent this limitation, inverted fluorescence microscopy is utilized in this work to investigate the SV response of the sensors at the micron-scale. In these diffusion experiments, oxygen concentration is measured by luminescence changes in regions with high SV constants and good linearity. Thus, we avoid numerical complexity of combining nonlinear SV equation with a diffusion model. This technique allows us to measure oxygen diffusion properties in different type of polymers like transparent, opaque, free-standing polymers and polymers that cannot be cast into free standing films and polymer composites.

In the second part of this thesis, we have explored the effect of Ag-Cu alloy nanoparticles on the emission intensity of luminophores at their close proximity. Alloy nanoparticles offer additional degrees of freedom for tuning their optical properties by altering atomic composition and atomic arrangement and thus can be an attractive option for manipulating signal of a wide range of luminophores. In this work, surface plasmon resonance spectrum of Ag-Cu alloy nanoparticles deposited by sputtering was easily tuned in wide wavelength range by varying one experimental condition- annealing temperature. Large metal enhanced luminescence for different luminophores viz Alexa Fluor 594 and Alexa Fluor 488 were achieved at the vicinity of Ag-Cu nanoparticles when maximum spectral overlap between SPR spectra of Ag-Cu nanoparticles and the emission and absorption spectra of the luminophores occur. We also studied the effect of composition of Ag-Cu nanoparticles synthesized by the polyol process on the luminescence of low quantum yield dye Cy3.

In the third part of this thesis, quenching effect of Cu nanoparticles on CdSe/ZnS nanocrystal quantum dots has been explored. As Cu nanoparticles have comparable dielectric properties with gold nanoparticles, they are expected to show similar quenching effects. It was found that Cu is an efficient quencher of fluorescence from CdSe/ZnS quantum dots and the quenching effect is due to resonance energy transfer from quantum dots to Cu nanoparticles.

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