RESUMO
Starting from commercially available 2-chloro-3-hydroxypyridine, a new route leading to the first protypical pentaarylpyridine bearing five different substituents is reported. This strategy involves a set of five sequential but fully regiocontrolled Suzuki-Miyaura reactions and highlights the 2-OBn pyridine protecting group as a key intermediate. The 2-OBn group played a double role: (i) it allowed additional bromination at position 5 and (ii) it could afford the reactive OTf species for the last C-arylation step at the less hindered 2 position of the tetraarylpyridine. The photophysical properties of the novel compounds are also described. The synthesized pentaarylpyridine derivative exhibit a large Stokes shift, strong solvatochromism, and quantum yield values up to 0.47; thus, they constitute promising building blocks for the design of environment-sensitive probes.
Assuntos
Piridinas/química , Piridinas/síntese química , Halogenação , Estrutura Molecular , EstereoisomerismoRESUMO
Fluorescence excitation-emission matrix (EEM) and synchronous scanning fluorescence (SF), coupled with parallel factor (PARAFAC) analysis, principal component analysis (PCA) and Linear discriminant analysis (LDA) methods were used to differentiate 49 lager beer samples and monitor the effects of temperature and sunlight exposition on their composition. EEMs were decomposed into independent fluorescent components. The beer samples were characterized by the presence of excitation/emission (exc/em) peaks at 290/350, 315/345, 340/410, 375/455, 360/420, 400/460, and 437/525 nm, which were ascribed, according to the known beer fluorescent components, respectively to aromatic amino acids, vitamin B6 (pyridoxal), vitamin B6 (pyridoxic acids), vitamin B3, iso-α-acids, vitamin B1, and vitamin B2. The variation of the relative concentration of iso-α-acids in the different beer brands presented the same trend with that of their relative IBU, thus revealing the potency of our method in the assessment of beer bitterness. The impact of temperature and sunlight was assessed by separately monitoring the modifications of the EEMs after 5 h exposition to 40°C temperature and sunlight respectively. Noticeably a variation of the peaks intensity of the iso-α-acids, carbonyl and polyphenols compounds were observed, accompanied by a decrease of the alcohol content, thus indicating beer aging. This method can be useful for the identification and monitoring of beer state during the technological production cycle and storage. PRACTICAL APPLICATION: The present work demonstrates the potency of the fluorescence technique used together with chemometric methods to give valuable information on beer bitterness. Development of rapid quantitative methods for beer bitterness assessment is of great importance for brewing industries.