Robert J. Twieg

Broadband terahertz characterization of the refractive index and absorption of some important polymeric and organic electro-optic materials

We report broad bandwidth, 0.1–10 THz time-domain spectroscopy of linear and electro-optic polymers. The common THz optical component materials high-density polyethylene, polytetrafluoroethylene, polyimide (Kapton), and polyethylene cyclic olefin copolymer (Topas) were evaluated for broadband THz applications. Host polymers polymethyl methacrylate, polystyrene, and two types of amorphous polycarbonate were also examined for suitability as host for several important chromophores in guest-host electro-optic polymer composites for use as broadband THz emitters and sensors.

A Photoactivatable Push−Pull Fluorophore for Single-Molecule Imaging in Live Cells

We have reengineered a red-emitting dicyanomethylenedihydrofuran push-pull fluorophore so that it is dark until photoactivated with a short burst of low-intensity violet light. Photoactivation of the dark fluorogen leads to conversion of an azide to an amine, which shifts the absorption to long wavelengths. After photoactivation, the fluorophore is bright and photostable enough to be imaged on the single-molecule level in living cells. This proof-of-principle demonstration provides a new class of bright photoactivatable fluorophores, as are needed for super-resolution imaging schemes that require active control of single molecule emission.

Superresolution imaging of targeted proteins in fixed and living cells using photoactivatable organic fluorophores

Superresolution imaging techniques based on sequential imaging of sparse subsets of single molecules require fluorophores whose emission can be photoactivated or photoswitched. Because typical organic fluorophores can emit significantly more photons than average fluorescent proteins, organic fluorophores have a potential advantage in super-resolution imaging schemes, but targeting to specific cellular proteins must be provided. We report the design and application of HaloTag-based target-specific azido DCDHFs, a class of photoactivatable push-pull fluorogens which produce bright fluorescent labels suitable for single-molecule superresolution imaging in live bacterial and fixed mammalian cells.

Three-dimensional superresolution colocalization of intracellular protein superstructures and the cell surface in live Caulobacter crescentus

Recently, single-molecule imaging and photocontrol have enabled superresolution optical microscopy of cellular structures beyond Abbe’s diffraction limit, extending the frontier of noninvasive imaging of structures within living cells. However, live-cell superresolution imaging has been challenged by the need to image three-dimensional (3D) structures relative to their biological context, such as the cellular membrane. We have developed a technique, termed superresolution by power-dependent active intermittency and points accumulation for imaging in nanoscale topography (SPRAIPAINT) that combines imaging of intracellular enhanced YFP (eYFP) fusions (SPRAI) with stochastic localization of the cell surface (PAINT) to image two different fluorophores sequentially with only one laser. Simple light-induced blinking of eYFP and collisional flux onto the cell surface by Nile red are used to achieve single-molecule localizations, without any antibody labeling, cell membrane permeabilization, or thiol-oxygen scavenger systems required. Here we demonstrate live-cell 3D superresolution imaging of Crescentin-eYFP, a cytoskeletal fluorescent protein fusion, colocalized with the surface of the bacterium Caulobacter crescentus using a double-helix point spread function microscope. Three-dimensional colocalization of intracellular protein structures and the cell surface with superresolution optical microscopy opens the door for the analysis of protein interactions in living cells with excellent precision (20–40 nm in 3D) over a large field of view (12 × 12 μm).

Stable amorphous blue phase of bent-core nematic liquid crystals doped with a chiral material

We report an induction of the blue phase III (BPIII) at a relatively low and wide (over 20 °C) temperature range in nematogenic achiral bent-core liquid crystals doped with a high twisting power chiral material. The pitch decreases with increasing chiral dopant ratio, and easily reaches the ultraviolet wavelength, so that completely dark texture is obtained under crossed polarizers. Electrooptical switching was achieved in a time range of a few to a few tens of milliseconds. We propose for the stabilization of BPIII that broad-temperature range smectic nano-clusters inhibit the long-range order of the double twisted helical structures, and also inhibit possible separation of chiral dopants from the mixture.

Copper-catalyzed amination of aromatic halides with 2-N, N-dimethylaminoethanol as solvent

A copper-catalyzed amination of aromatic halides under mild conditions using N,N-dimethylaminoethanol as solvent is described. We have studied this reaction in some detail varying the copper source, base, water content and other parameters including the scope of useful amine and aromatic halide structures. A variety of 4-halo-N,N-cycloalkylanilines and 2-N,N-cycloalkylaminothiophenes were synthesized for further elaboration into chromophores for optoelectronic applications.

Low Threshold Lasing in Cholesteric Liquid Crystals

Abstract Cholesteric liquid crystals, due to their periodic structure and large birefringence, are 1-d photonic band-gap materials. Circularly polarized light of the same handedness as the cholesteric structure cannot propagate in the reflection band. We have studied the effects of this band-gap structure on the fluorescence spectrum of dyes dissolved in the cholesteric liquid crystal, as well as on the fluorescence spectrum of the liquid crystal itself. We have found that emission is enhanced at the band edges, and, above a certain pump threshold, lasing occurs both in dye-doped and in pure liquid crystals. Extremely low lasing thresholds and high efficiencies were observed in dye-doped systems. The results suggest an active energy transfer mechanism between the LC host and the fluorescent dye molecules.

Azido Push-Pull Fluorogens Photoactivate to Produce Bright Fluorescent Labels

Dark azido push-pull chromophores have the ability to be photoactivated to produce bright fluorescent labels suitable for single-molecule imaging. Upon illumination, the aryl azide functionality in the fluorogens participates in a photochemical conversion to an aryl amine, thus restoring charge-transfer absorption and fluorescence. Previously, we reported that one compound, DCDHF-V-P-azide, was photoactivatable. Here, we demonstrate that the azide-to-amine photoactivation process is generally applicable to a variety of push-pull chromophores, and we characterize the photophysical parameters including photoconversion quantum yield, photostability, and turn-on ratio. Azido push-pull fluorogens provide a new class of photoactivatable single-molecule probes for fluorescent labeling and super-resolution microscopy. Lastly, we demonstrate that photoactivated push-pull dyes can insert into bonds of nearby biomolecules, simultaneously forming a covalent bond and becoming fluorescent (fluorogenic photoaffinity labeling).

["Λ-like chromophores for chiral non-linear optical materials"]

Abstract The first hyperpolarizability of several Λ -like chromophores including Malachite Green and Brilliant Green were measured by means of Kleinman-disallowed hyper-Rayleigh (harmonic light) scattering (KD-HRS). Such chromophores are of interest as components of a new class of chiral and axial macroscopic materials. Light scattering measurements were carried out in both the non-resonant and the anomalous dispersion regime in order to compare experimental results with a two-level model that indicates that B-symmetry excited states will contribute. Large hyperpolarizabilities were observed in all cases and evidence that the lowest-lying excited state has B-symmetry was found in some molecules.

Short-Range Smectic Order in Bent-Core Nematic Liquid Crystals

Small angle X-ray diffraction from the uniaxial nematic phase of certain bent-core liquid crystals is shown to be consistent with the presence of molecular clusters possessing short-range tilted smectic (smectic-C) order. Persistence of these clusters throughout the nematic phase, and even into the isotropic state, likely accounts for the unusual macroscopic behavior previously reported in bent-core nematics, including an anomalously large flexoelectric effect (∼ 1000 times that of conventional calamitic nematics), very large orientational and flow viscosities (∼ 10–100 and ∼ 100–1000 times, respectively, typical values for calamitics), and an extraordinary flow birefringence observed in the isotropic state.