Jeffery E. Raymond

Conjugation-induced fluorescent labeling of proteins and polymers using dithiomaleimides.

Dithiomaleimides (DTMs) with alkyl substituents are shown to be a novel class of highly emissive fluorophores. Variable solubility and further functionalization can easily be tailored through the choice of N and S substituents. Inclusion of a DTM unit into a ROP/RAFT initiator or insertion into the disulfide bond of salmon calcitonin (sCT) demonstrates the utility for fluorescent labeling of polymers and proteins. Simultaneous PEGylation and fluorescent labeling of sCT is also demonstrated, using the DTM unit as both a linker and a fluorophore. It is anticipated that DTMs will offer an attractive alternative to commonly used bulky, planar fluorophores.

Synthesis and Two-Photon Absorption Enhancement of Porphyrin Macrocycles

Improving the nonlinear optical properties of organic materials through transition to macromolecular architectures of highly conjugated chromophores has been shown to be a viable strategy for generating materials suitable for TPA applications. In this study we display a simple and elegant method by which to synthesize macrocycles of porphyrin dimers. Two-photon absorption studies show 2 orders of magnitude enhancement of cross-section of the material, giving a maximum delta(2) of 10(6) GM.

New functional handle for use as a self-reporting contrast and delivery agent in nanomedicine.

The synthesis and photophysical characterization of a chromophore-bridged block copolymer system is presented. This system is based on a dithiomaleimide (DTM) functional group as a highly emissive functionality which can readily be incorporated into polymeric scaffolds. A key advantage of this new reporter group is its versatile chemistry, ease of further functionalization, and notably small size, which allows for ready incorporation without affecting or disrupting the self-assembly process critical to the formation of core-shell polymeric contrast and drug delivery agents. We demonstrate the potential of this functionality with a diblock system which has been shown to be appropriate for micellization and, when in the micellar state, does not self-quench. The block copolymer is shown to be significantly more emissive than the lone dye, with a concentration-independent emission and anisotropy profile from 1.5 mM to 0.15 μM. An emission lifetime and anisotropy decay comparison of the block copolymer to its micelle displays that time-domain fluorescence lifetime imaging (FLIM) is able to rapidly resolve differences in the supramolecular state of this block-dye-block polymer system. Furthermore, the ability to resolve these differences in the supramolecular state means that the DTM micelles are capable of self-reporting when disassembly occurs, simply by monitoring with FLIM. We demonstrate the great potential for in vitro applications that this system provides by using FLIM to observe micelle disassembly in different vascular components of rat hippocampal tissue. In total this system represents a new class of in-chain emitter which is appropriate for application in quantitative imaging and the tracking of particle degradation/disassembly events in biological environments.

Quantitative non-linear optical imaging in the nano-regime

The development of functional solid state non-linear optical (NLO) systems for device applications is critical to several fields. Optical computing, laser hardening, 3-dimensional data storage and remote sensing are just a few of the areas advanced by the characterization of new NLO systems. One promising venue for the development of these technologies is the nano-/meso-scale self assembly of viable chromophores into tunable aggregates. Here we present a method by which individual aggregates can be quantitatively imaged by two photon fluorescence near field scanning optical microscopy (NSOM).

Short Communication: Room-Temperature Growth of Carbon Nanofibers From Iron-Encapsulated Dendritic Catalysts

Ordered carbonaceous growth typically requires high-energy methods such as arc discharge [1] or decomposition of hydrocarbon-based precursors using laser [2–4], plasma [3], or thermolytic techniques [4]. For the latter technique, temperature regimes on the order of 600–1000° C are most common, with a few recent reports citing lower temperatures using halogenated precursors [5–7], or through alkali-metal catalyzed transformation of bulk carbon allotropes [8,9]. Sailor etal. have reported the first growth of non-amorphous carbon deposits at room temperature [10]. However, their electrochemical synthesis did not produce nanostructural carbon; due to the absence of nanosized catalytic seeds, the diameters of their fibers were > 5μm, and contained copious amounts of Cl, H, N, and O impurities.