Impact of temperature and sunlight exposition on locally brewed beers composition revealed by fluorescence spectroscopy coupled with chemometric methods.

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.

Antioxidant Properties of Lapachol and Its Derivatives and Their Ability to Chelate Iron (II) Cation: DFT and QTAIM Studies.

The elucidation of the complexation of lapachol and its derivatives to Fe2+ cation has been done using the density functional theory (DFT). This complexation has been limited to bidentate and tridentate to Fe2+ cation. Geometry optimizations have been implemented in gas and solution phase (water, acetonitrile, chlorobenzene, benzene, and toluene) for ligands at B3LYP/6-311++G (d,p) level of theory using B3LYP/6-31+G(d,p) optimized data as starting point. But, the geometrical optimizations in solution phase of the 22 complexes analyzed of lapachol and its derivatives to Fe2+ cation were restricted to acetonitrile and benzene. The complexation energy and the metal ion affinity (MIA) have also been calculated using the B3LYP method. The results obtained indicated a proportionality between the MIA values and the retained charge on Fe2+ cation for k 2-(O1,O2) modes. But, an inverse proportionality has been yielded between these two parameters for k 3-(O2, C=C) tridentate modes. For k3-(O3,C=C) tridentate mode coordination, the higher stability has been obtained. In this latter tridentate coordination in gas phase, the topological analysis of complexes exhibits the fact that the electron density is concentrated between the O3 oxygen atom of the ligand attached to Fe2+ and this metal cation. Moreover, the hydrogen bond strength calculated for isolated ligands (situated between 23.92 and 30.15 kJ/mol) is in the range of normal HBs. Collectively, all the complexation processes have shown to be highly exothermic. Our results have also shown that the electron extraction from Fe 2+ ...La i complexes is more difficult compared to that from free ligands.

Electronic transitions and ESIPT kinetics of the thienyl-3-hydroxychromone nucleobase surrogate in DNA duplexes: a DFT/MD-TDDFT study.

The fluorescent nucleobase surrogate M (2-thienyl-3-hydroxychromone fluorophore) when imbedded in DNA opposite an abasic site exhibits a two colour response highly sensitive to environment changes and base composition. Its two colour emission originates from an excited state intramolecular proton transfer (ESIPT), which converts the excited normal N* form into its T* tautomer. To get deeper insight on the spectroscopic properties of M in DNA duplexes, quantum chemical calculations were performed on M stacked with different base pairs in model trimers extracted from MD simulations. The photophysics of M in duplexes appeared to be governed by stacking interactions as well as charge and hole transfer. Indeed, stacking of M in DNA screens M from H-bonding with water molecules, which favours ESIPT and thus, the emission of the T* form. With A and T flanking bases, the electronic densities in the frontier MOs were localized on M, in line with its effective absorption and emission. In addition, reduction of the free rotation between the thienyl and chromone groups together with the shielding of the dye from water molecules largely explain its enhanced quantum yield in comparison to the free M in solution. By contrast, the localisation of the electron density on the flanking G residues in the ground state and the energetically favorable hole transfer from M to G in the excited state explains the reduced quantum yield of M sandwiched between CG pairs. Finally, the much higher brightness of M as compared to 2-aminopurine when flanked by A and T residues could be related to the much stronger oscillator strength of its S0 → S1 transition and the ineffective charge transfer from M to A or T residues.

Dynamics of kink-dark solitons in Bose-Einstein condensates with both two- and three-body interactions.

The matter-wave solutions of Bose-Einstein condensates with three-body interaction are examined through the one-dimensional Gross-Pitaevskii equation. By using a modified lens-type transformation and a further extension of the tanh-function method we obtain the exact analytical solutions which describe the propagation of kink-shaped solitons, anti-kink-shaped solitons, and other families of solitary waves. We realize that the shape of a kink solitary wave depends on both the scattering length and the parameter of atomic exchange with the substrate. The stability of the solitary waves is examined using analytical and numerical methods. Our results can also be applied to nonlinear optics in the presence of cubic-quintic media.