Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays.

High quantum yield NIR fluorophores are rare. Factors that drive low emission quantum yields at long wavelength include the facts that radiative rate constants increase proportional to the cube of the emission energy, while nonradiative rate constants increase in an approximately exponentially with decreasing S-S energy gaps (in accordance with the energy gap law). This work demonstrates how the proquinoidal BTD building blocks can be utilized to minimize the extent of excited-state structural relaxation relative to the ground-state conformation in highly conjugated porphyrin oligomers, and shows that 4-ethynylbenzo[][1,2,5]thiadiazole () units that terminate -to- ethyne-bridged (porphinato)zinc () arrays, and 4,7-diethynylbenzo[][1,2,5]thiadiazole () spacers that are integrated into the backbone of these compositions, elucidate new classes of impressive NIR fluorophores.

Real-time dose-rate monitoring with gynecologic brachytherapy: Results of an initial clinical trial.

Purpose: A nanoscintillator-based fiber-optic dosimeter (nanoFOD) was developed to measure real-time dose rate during high-dose-rate (HDR) brachytherapy. A trial was designed to prospectively test clinical feasibility in gynecologic implants.

Methods And Materials: A clinical trial enrolled women undergoing vaginal cylinder HDR brachytherapy.

Fiber-optic detector for real time dosimetry of a micro-planar x-ray beam.

Purpose: Here, the authors describe a dosimetry measurement technique for microbeam radiation therapy using a nanoparticle-terminated fiber-optic dosimeter (nano-FOD).

Methods: The nano-FOD was placed in the center of a 2 cm diameter mouse phantom to measure the deep tissue dose and lateral beam profile of a planar x-ray microbeam.

Results: The continuous dose rate at the x-ray microbeam peak measured with the nano-FOD was 1.

Europium- and lithium-doped yttrium oxide nanocrystals that provide a linear emissive response with X-ray radiation exposure.

Eu- and Li-doped yttrium oxide nanocrystals [Y2-xO3; Eux, Liy], in which Eu and Li dopant ion concentrations were systematically varied, were developed and characterized (TEM, XRD, Raman spectroscopic, UV-excited lifetime, and ICP-AES data) in order to define the most emissive compositions under specific X-ray excitation conditions. These optimized [Y2-xO3; Eux, Liy] compositions display scintillation responses that: (i) correlate linearly with incident radiation exposure at X-ray energies spanning from 40-220 kVp, and (ii) manifest no evidence of scintillation intensity saturation at the highest evaluated radiation exposures [up to 4 Roentgen per second]. For the most emissive nanoscale scintillator composition, [Y1.

Dual energy converting nano-phosphors: upconversion luminescence and X-ray excited scintillation from a single composition of lanthanide-doped yttrium oxide.

We report an upconverting nanomaterial composition, [Y(2)O(3); Yb (2%), Er (1%)], that converts both X-ray and high-fluence NIR irradiation to visible light. This composition is compared to a higher Yb(3+) doped composition, [Y(2)O(3); Yb (10%), Er (1%)], that displays diminished visible X-ray scintillation, but shows enhanced red wavelength centered upconversion emission. These nanocrystals have been characterized by TEM, X-ray diffraction, power-dependent upconversion luminescence, and X-ray scintillation spectroscopy.

Effect of solvent polarity and electrophilicity on quantum yields and solvatochromic shifts of single-walled carbon nanotube photoluminescence.

In this work, we investigate the impact of the solvation environment on single-walled carbon nanotube (SWCNT) photoluminescence quantum yield and optical transition energies (E(ii)) using a highly charged aryleneethynylene polymer. This novel surfactant produces dispersions in a variety of polar solvents having a wide range of dielectric constants (methanol, dimethyl sulfoxide, aqueous dimethylformamide, and deuterium oxide). Because a common surfactant can be used while maintaining a constant SWCNT-surfactant morphology, we are able to straightforwardly evaluate the impact of the solvation environment upon SWCNT optical properties.

Structural and pH dependence of excited state PCET reactions involving reductive quenching of the MLCT excited state of [RuII(bpy)2(bpz)]2+ by hydroquinones.

The proton-coupled electron transfer (PCET) reaction between the bpz-based photoexcited (3)MLCT state of [Ru(II)(bpy)(2)(bpz)](2+) (bpy = 2,2'-bipyridine, bpz = 2,2'-bipyrazine) and a series of substituted hydroquinones (H(2)Q) has been studied by transient absorption (TA) and time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X-band. When the reaction is carried out in a CH(3)CN/H(2)O mixed solvent system with unsubstituted hydroquinone, the neutral semiquinone radical (4a) and its conjugate base, the semiquinone radical anion (4b), are both observed. Variation of the acid strength in the solvent mixture allows the acid/base dependence of the PCET reaction to be investigated.