Development of Certified Reference Material Solutions for Phytochemicals in Ginger and Kava.

BACKGROUND: Dietary supplements derived from botanicals are commonly consumed and investigated in biomedical studies for their potential health benefits. Accurate identification and quantification of key chemical constituents from botanical ingredients is necessary for consistent product preparations and reproducible research results. Manufacturers need quantitative reference materials of the chemical constituents of interest to verify the content of ingredients and products. The rigor and reproducibility of biomedical research is enhanced through thorough characterization of the interventions used in mechanistic, clinical, and safety investigations. Quantitative reference materials enable reliable product quality assessments and reproducible research results. OBJECTIVE: Solution-based certified reference material (CRM) mixes were developed as calibrants for phytochemicals in ginger and kava. The kava CRM contained yangonin, desmethoxyyangonin, dihydrokavain, DL-kavain, methysticin, dihydromethysticin, flavokawain A, flavokawain B, and flavokawain C. The ginger CRM contained 6-gingerol, 8-gingerol, 10-gingerol, 6-shogaol, 8-shogaol, and 10-shogaol. METHODS: Each phytochemical was sourced as an isolated compound and assigned a purity factor by a mass balance approach accounting for residual impurities. The solution standard mixes were formulated by gravimetric addition of each phytochemical incorporating the purity factor and diluting with acetonitrile to the target concentrations of 500 µg/mL for the gingerols and shogaols, 250 µg/mL for the kavalactones, and 25 µg/mL for the flavokawains. RESULTS: The concentration accuracy of each component in the solution mixes was analytically verified by ultra high performance liquid chromatography with ultraviolet detection (UHPLC-UV) assay comparison to an independently prepared calibration solution. Each component in the ginger and kava CRMs were within 5 and 7% of the target concentrations, respectively. CONCLUSION: Homogeneous kava and ginger phytochemical solution mixes were produced with accurate constituent concentrations and demonstrated good stability over 2 years. These solution mixes were launched as commercially available CRMs. HIGHLIGHTS: These mixes can be used as accurate concentration stock solutions to prepare calibrators and controls for botanical dietary supplement product testing and standardization.

Resonance Raman Spectroscopy of the T1 Triplet Excited State of Oligothiophenes.

The characterization of triplet excited states is essential for research on organic photovoltaics and singlet fission. We report resonance Raman spectra of two triplet oligothiophenes with n-alkyl substituents, a tetramer and hexamer. The spectra of the triplets are more complex than the ground state, and we find that density functional theory calculations are a useful starting point for characterizing the bands. The spectra of triplet tetrathiophene and hexathiophene differ significantly from one another. This observation is consistent with a T1 excitation that is delocalized over at least five rings in long oligomers. Bands in the 500-800 cm(-1) region are greatly diminished for an aggregated sample of hexathiophene, likely caused by fast electronic dephasing. These experiments highlight the potential of resonance Raman spectroscopy to unequivocally detect and characterize triplets in thiophene materials. The vibrational spectra can also serve as rigorous standards for evaluating computational methods for excited-state molecules.

Anion-dependent self-assembly of near-infrared luminescent 24- and 32-metal Cd-Ln complexes with drum-like architectures.

Two series of 4d-4f clusters [Ln8Cd24L12(OAc)48] and [Ln6Cd18L9Cl8(10)(OAc)28(26)] (Ln = Nd, Gd, Er, and Yb) with novel drum-like structures were prepared using a flexible Schiff base ligand. Their NIR luminescence properties were determined.

The effects of aggregation on electronic and optical properties of oligothiophene particles.

Solution processing of oligothiophene molecules is shown to produce a range of particles with distinct morphologies. Once isolated on a substrate, the optical and electronic properties of individual particles were studied. From polarized scanning confocal microscopy experiments, distinct particles that are identifiable by shape were shown to have similar emission spectra except in regard to the 0-0 vibronic band intensity. This suppression of the 0-0 vibronic band correlates to the amount of energetic disorder present in a weakly coupled H-aggregate. The studied particles ranged from moderate to almost complete suppression of the 0-0 vibronic band when compared to the emission spectrum of the isolated molecule in solution. All particles were found to have a high degree of geometric order (molecular alignment) as observed from the fluorescence dichroism (FD) values of around 0.7-0.8 for all the studied morphologies. The structural and electronic properties of the particles were investigated with Kelvin probe force microscopy (KPFM) to measure the local contact potential (LCP) difference, a quantity that is closely related to the differences in intermolecular charge distribution between the oligothiophene particles. The LCP was found to vary by as much as 70 mV between different oligothiophene particles and a trend was observed that correlated the LCP changes with the amount of energetic disorder present, as signified by the suppression of the 0-0 vibronic peak in the emission spectra. Combined polarized scanning confocal microscopy studies, along with KPFM measurements, help to provide fundamental insights into the role of morphology, molecular packing, and intermolecular charge distributions in oligiothiophene particles.

Synthesis, characterization, and photophysical properties of a thiophene-functionalized bis(pyrazolyl) pyridine (BPP) tricarbonyl rhenium(I) complex.

A bromo tricarbonyl rhenium(I) complex with a thiophene-functionalized bis(pyrazolyl) pyridine ligand (L), ReBr(L)(CO)(3) (1), has been synthesized and characterized by variable temperature and COSY 2-D (1)H NMR spectroscopy, single-crystal X-ray diffraction, and photophysical methods. Complex 1 is highly luminescent in both solution and solid-state, consistent with phosphorescence from an emissive (3)MLCT excited state with an additional contribution from a LC (3)(pi-->pi*) transition. The single-crystal X-ray diffraction structure of the title ligand is also reported.