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The design and synthesis of a family of calixarene-based nonlinear optical (NLO) chromophores are discussed. The calixarene chromophores are macrocyclic compounds consisting of four simple D-π-A units bridged by methylene groups. These molecules were synthesized such that four D-π-A units of the calixarene were aligned along the same direction with the calixarene in a cone conformation. These nonlinear optical super-chromophores were subsequently fabricated into covalently bound self-assembled monolayers on the surfaces of fused silica and silicon. Spectroscopic second harmonic generation (SHG) measurements were carried out to determine the absolute value of the dominant element of the second-order nonlinear susceptibility, d33, and the average molecular alignment, ψ. We find a value of d33 = 60 pm/V at a fundamental wavelength of 890 nm, and ψ˜ 36° with respect to the surface normal.
We report here a procedure for the functioalization of SiO2-coated, SiONx waveguides for biological assays. Surface functionalization occurs by self-assembly of an amine-terminated silane monolayer on the waveguide, followed by partial chemical modification with functionalized polyethylene glycol (PEG) groups. Functionalized surfaces were characterized by atomic force microscopy and contact angle measurements. When combined with a BSA blocking step, these functional PEG surfaces significantly reduced non-specific binding and allowed for specific binding to occur. An antibody sandwich assay for detection of Bacillus anthracis protective antigen was used to validate these surfaces for sensing applications.
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