Biomedical subjects

Samuel A Bryan

Publications and source records attributed to Samuel A Bryan.

3 recordsLinked to original sources

PubMed2006

Highly oxidizing excited states of Re and Tc complexes.

Like the Re analogue, the ligand-to-metal charge transfer (LMCT) excited-state of [Tc(dmpe)3]2+ (dmpe is bis-1,2-(dimethylphosphino)ethane) is luminescent in solution at room temperature. Surprisingly, both [M(dmpe)3]2+* species have extremely large excited-state potentials (ESPs) as oxidants-the highest for any simple coordination complex of a transition metal. Furthermore, this potential is available using a photon of visible light (calculated for M = Re(Tc); E1/2* = +2.61(2.52) V versus SCE; lambdamax = 526(585) nm). Using a Rehm-Weller analysis with a series of aromatic hydrocarbons as electron-transfer quenchers, E1/2(Re2+*/Re+) has been determined to be 2.58 V, in good agreement with the calculated value. Both [M(dmpe)3]2+* species are quenched by chloride ion and both can function as excited-state oxidants in water solution.

Organometallic Compounds↗

PubMed2005

Luminescence from the trans-dioxotechnetium(V) chromophore.

The luminescence of trans-[TcO2(L)4]+ (L = pyridine (py) or picoline (pic)) and trans-[TcO2(CN)4]3- at room and low temperature is described and represents the first example of room temperature excited-state luminescence observed for Tc complexes. At room temperature, the complexes exhibited broad luminescence with emission maxima ranging from 745 to 780 nm. Analogous to the Re complexes (emission at 635-655 nm), the low-temperature emission spectra of microcrystalline samples of [TcO2(py)4]BPh4 and [TcO2(pic)4]BPh4 display the characteristic progressions of the symmetric O=Tc=O and Tc-L stretching modes. DFT/TDDFT calculations were performed on the trans-[MO2(L)4]+ (M = Re, Tc) congeners and predicted the dioxotechnetium emission to be 0.41 eV lower in energy than its Re analogue. Low-temperature lifetimes (8 K) ranging from 15 to 1926 mus for the series of Tc complexes are consistent with the Re analogues.

Journal Article↗

PubMed2003

Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device. 11. Design and evaluation of a small portable sensor for the determination of ferrocyanide in Hanford waste samples.

A portable spectroelectrochemical sensor has been designed, evaluated, and demonstrated on a complex sample of radioactive waste. The sensor consisted of a black delrin sample compartment with a total internal sample volume of 800 microL, attached to an indium tin oxide coated glass multiple internal reflection optical element. Detection was by total internal reflection of light from a blue light emitting diode source. After a 10 min uptake for each standard, the sensor showed a linear response in absorbance change for 5 x 10(-5) to 5 x 10(-3) M ferrocyanide with electrochemical modulation by scanning at 20 mV/s from -0.30 V to +0.55 V vs a Ag/AgCl reference electrode. Due to the complex nature of Hanford radioactive tank waste samples containing ferrocyanide, a standard addition method was developed for analysis. The spectroelectrochemical sensor determined a concentration of 9.2 mM ferrocyanide for U-Plant-2 simulant solution containing 9.38 mM ferrocyanide that was prepared according to Hanford process flowsheets. A radioactive tank waste sample from Hanford Tank 241-C-112 was determined to be 1.0 mM in ferrocyanide using the spectroelectrochemical sensor. A value for the ferrocyanide concentration in the sample of 0.61 mM was determined by FTIR spectroscopy.

Electrochemistry↗