Solid state NMR and DFT studies of azo-hydrazone tautomerism in azo dyes and chitosan-dye films.

The properties of materials containing azobenzene depend strongly on the dynamics of and isomerization which in turn are influenced by the presence of different possible tautomers. Two commonly used food azo dyes, Allura Red (ALR) and Amaranth (AMA), were studied by NMR spectroscopy to experimentally determine their tautomeric forms and then theoretically rationalized. Variable temperature 2D H-N HMBC NMR provided a direct measure of the hydrazone percentage of the dyes in solution which was complimented by H ultrafast magic-angle spinning (MAS) and C CPMAS solid state NMR to characterize the structures of the solid dyes alone and incorporated into chitosan films designed to disassemble upon exposure to light and water.

A cautionary tale of basic azo photoswitching in dichloromethane finally explained.

Many studies of azobenzene photoswitches are carried out in polar aprotic solvents as a first principles characterization of thermal isomerization. Among the most convenient polar aprotic solvents are chlorinated hydrocarbons, such as DCM. However, studies of azobenzene thermal isomerization in such solvents have led to spurious, inconclusive, and irreproducible results, even when scrupulously cleaned and dried, a phenomenon not well understood.

Chitosan-azo dye bioplastics that are reversibly resoluble and recoverable under visible light irradiation.

Biopolymer composite materials were prepared by combining bio-sourced cationic water-soluble chitosan with bi-functional water-soluble anionic azo food dyes amaranth (AMA) or allura red (ALR) as ionic cross-linkers, mixing well in water, and then slow-drying in air. The electrostatically-assembled ionically-paired films showed good long-term stability to dissolution, with no re-solubility in water, and competitive mechanical properties as plastic materials. However, upon exposure of the bioplastics to low power light at sunlight wavelengths and intensities stirring in water, the stable materials photo-disassembled back to their water-soluble and low-toxicity (edible) constituent components, structural photo-isomerization of the azo ionic crosslinkers.

Investigation of cyanine-based infrared dyes as calibrants in radiochromic films.

Background: Radiochromic material such as lithium pentacosa-10,12-diynoate (LiPCDA) has been suggested as the radiation-sensitive material for real-time in vivo fiber-optic dosimetry. In this configuration, micron-thick radiochromic coating would measure the absorbed dose, where a major challenge is the uncertainty in the active material thickness, necessitating calibration. A homogeneously incorporated inert infrared (IR) dye, which must also be stable in ambient conditions and against radiolysis, can be added to the radiochromic film to enable optical calibration.

Optical and computational study of the ↔ reversible isomerization of the commercial bis-azo dye Bismarck Brown Y.

The -- isomerization behaviour of Bismarck Brown Y (BBY) during and after irradiation with visible light, was characterized in detail for the first time by means of optical pump-probe experiments, to study the geometric inter-conversion of bis-azobenzene both in solution and embedded in multi-layered polymeric thin films. The rate constants observed for the thermal - back isomerization permit a determination of how the thermal isomerization is influenced by its local environment. In both solution and when incorporated into multi-layered thin films, the thermal relaxation observed for the commercial azo dye BBY showed a highly unusual biexponential decay, which clearly demonstrates two distinct isomerization processes.

A SiPM-Enabled Portable Delayed Fluorescence Photon Counting Device: Climatic Plant Stress Biosensing.

A portable and sensitive time-resolved biosensor for capturing very low intensity light emission is a promising avenue to study plant delayed fluorescence. These weak emissions provide insight on plant health and can be useful in plant science as well as in the development of accurate feedback indicators for plant growth and yield in applications of agricultural crop cultivation. A field-based delayed fluorescence device is also desirable to enable monitoring of plant stress response to climate change.

Role of water in the crystal structure of LiPCDA monomer and the radiotherapy dose response of EBT-3 film.

Purpose: Radiochromic material used in recent commercial films has been suggested as a candidate for in vivo dosimetry because of its dose sensitivity, real-time response, and atomic composition. It was observed that its sensitive material, lithium pentacosa-10,12-diynoate (LiPCDA), can have two distinct forms, with main absorbance peaks at ∼635 and ∼674 nm. The spectrum of the latter is similar to that of pentacosa-10,12-diynoic acid (PCDA) used in the commercial predecessor, obtained through desiccation of the commercial film.

Theory and experiment of chain length effects on the adsorption of polyelectrolytes onto spherical particles: the long and the short of it.

We study here the role of polyelectrolyte chain length, that is number of repeat units (mers), in the competitive adsorption of a simple model polyanion, poly(acrylic acid), onto 85 nm spherical silica particles capped with a model polycation, poly(allylamine hydrochloride). Performing fluorescence spectroscopy experiments, we measured chain-length dependence of dilute aqueous polyelectrolyte adsorption, at full surface coverage, onto an oppositely charged polyelectrolyte overtop spherical silica nanoparticles (10-3 g L-1). Preferential adsorption was determined by comparing the characteristic fluorescence intensities of the two fluorophore-labeled and narrowly disperse polyacrylic acid samples (NMA-PAA450k and Dan-PAA2k) of 450k- and 2k-molecular weight (6250- and 28-mers), respectively.

Effect of laser pulse shaping on photoacoustic dosimetry in retinal models.

Photoacoustic sensing can be a powerful technique to obtain real-time feedback of laser energy dose in treatments of biological tissue. However, when laser therapy uses pulses with microsecond duration, they are not optimal for photoacoustic pressure wave generation. This study examines a programmable fiber laser technique using pulse modulation in order to optimize the photoacoustic feedback signal to noise ratio (SNR) in a context where longer laser pulses are employed, such as in selective retinal therapy.

Potential of sub-microsecond laser pulse shaping for controlling microcavitation in selective retinal therapies.

Pilot results showing the potential of sub-microsecond laser pulse shaping to optimize thermomechanical confinement in laser-tissue interactions involving microcavitation are presented. Model samples based on aqueous suspensions of retinal melanosomes and eumelanin particles were irradiated at 532 nm with nanosecond laser pulses and picosecond laser pulse trains having differing shapes and durations. The cavitation threshold radiant exposure and the bubble lifetime above the threshold were measured using a pump-probe setup and sub-nanosecond time-resolved imaging.

Toward an automated method for optical coherence tomography characterization.

With the increasing use of optical coherence tomography (OCT) in biomedical applications, robust yet simple methods for calibrating and benchmarking a system are needed. We present here a procedure based on a calibration object complemented with an algorithm that analyzes three-dimensional OCT datasets to retrieve key characteristics of an OCT system. The calibration object combines state-of-the-art tissue phantom material with a diamond-turned aluminum multisegment mirror.

Towards a bimodal proximity sensor for in situ neurovascular bundle detection during dental implant surgery.

Proof of concept results are presented towards an in situ bimodal proximity sensor for neurovascular bundle detection during dental implant surgery using combined near infrared absorption (NIR) and optical coherence tomography (OCT) techniques. These modalities are shown to have different sensitivity to the proximity of optical contrast from neurovascular bundles. NIR AC and DC signals from the pulsing of an artery enable qualitative ranging of the bundle in the millimeter range, with best sensitivity around 0.

Microflow1, a sheathless fiber-optic flow cytometry biomedical platform: demonstration onboard the international space station.

A fiber-optic based flow cytometry platform was designed to build a portable and robust instrument for space applications. At the core of the Microflow1 is a unique fiber-optic flow cell fitted to a fluidic system and fiber coupled to the source and detection channels. A Microflow1 engineering unit was first tested and benchmarked against a commercial flow cytometer as a reference in a standard laboratory environment.

High-throughput cellular screening of engineered ECM based on combinatorial polyelectrolyte multilayer films.

The capacity to engineer the extracellular matrix is critical to better understand cell function and to design optimal cellular environments to support tissue engineering, transplantation and repair. Stacks of adsorbed polymers can be engineered as soft wet three dimensional matrices, with properties tailored to support cell survival and growth. Here, we have developed a combinatorial method to generate coatings that self assemble from solutions of polyelectrolytes in water, layer by layer, to produce a polyelectrolyte multilayer (PEM) coating that has enabled high-throughput screening for cellular biocompatibility.

Effect of liposomal confinement on photothermal and photo-oximetric fluorescence lifetimes of photosensitizers with varying hydrophilicity.

The time-resolved fluorescence of photosensitizers (PSs) of varying hydrophobicities, di-and tetrasulfonated Al phthalocyanines (Al-2 and Al-4), and Photochlor (HPPH), was investigated in liposomes used as cell-mimetic models. Using frequency-and time-domain apparatus, the fluorescence lifetime, tau(fluo), was compared for PSs free in aqueous solution and in a liposome-associated state at varied temperatures (25 to 78 degrees C) and oxygen concentrations (0-190 microM). The analysis of tau(fluo) revealed different decay behaviors for the free-solution and liposome-confined PSs, most significantly for the lipophilic HPPH.