DFT investigation on the structural and vibrational behaviours of the non-protein amino acids in hybrid explicit/continuum solvent: a case of the zwitterions γ-aminobutyric and α - aminoisobutyric acids.

BACKGROUND: The influence of hybrid solvation models on the molecular structures and vibrational characteristics of g-aminobutyric acid (GABA) and a-aminoisobutyric acid (AIB) zwitterions was assessed by employing a variety of Density Functional Theory (DFT). The quantum chemical methods included the B3LYP and B3PW91 hybrid functionals and the 6­311++G(d,p) basis set. METHODS: The most stable conformation derived from the potential energy surface (PES) scans using the B3LYP/6-311++G(d,p) model chemistry for each studied molecule was predicted within a continuum environment represented by the COSMO and SMD solvation models. The stable structures were subsequently immersed in explicit/COSMO and explicit/SMD hybrid solvation models, where 10 and 8 water molecules were explicitly positioned around the functional groups of the GABA and AIB zwitterions, respectively. The number of water molecules chosen was sufficient to prevent proton transfer among the carboxylate group (COO-) and the ammonium group (NH3+) within each molecule under investigation. After optimizing the geometry of each hydrated complex, the normal vibrational modes were determined. The scaled theoretical frequencies obtained from the various model chemistries were then compared to available experimental data from infrared (IR) and Raman spectroscopy. RESULTS: In the case of GABA and AIB molecules, the comparisons revealed that the B3LYP/6-311++G(d,p) model chemistry yielded wavenumber values that closely matched the experimental IR and Raman data, particularly when the explicit/SMD solvent was employed. The computed results indicate deviations of less than 4% when compared to the experimental data for the two molecules under investigation.

Spectroscopic, quantum chemical, molecular docking and molecular dynamics investigations of hydroxylic indole-3-pyruvic acid: a potent candidate for nonlinear optical applications and Alzheimer's drug.

In this paper, a complete theoretical investigation of hydroxylic indole-3-pyruvic acid (HIPyA) molecule was performed using the DFT quantum chemical, molecular docking and molecular dynamics calculations. The conformational analysis of HIPyA molecule was carried out using density functional theory quantum chemical calculations. The most stable structure of the studied molecule was predicted by means of DFT/B3LYP method with cc-pVTZ basis set. The simulated vibrational frequencies were assigned and proved to be in agreement with the available experimental FT-IR data. The effects of gas phase and solvents on UV-visible spectra of HIPyA molecule were simulated using TD-DFT/B3LYP method with cc-pVTZ basis set. The analysis of the density of states spectrum validates the frontier molecular orbitals results, which reveals the charge transfer interaction in HIPyA molecule. The molecular electrostatic potential surface confirms the electrophilic and nucleophilic reactive sites of the studied molecule. The natural bond orbital analysis evidences the bioactivity of the studied molecule. The obtained first order hyperpolarizability value is 33.596 times greater than urea, which confirms the nonlinear optical activity of HIPyA molecule. The molecular docking analysis reveals that the studied molecule under interest can act as a potent inhibitor against the amyloid ß-protein (Aß) enzyme, which causes the Alzheimer's disease. The molecular dynamics analysis confirms the reliability of the docking results.Communicated by Ramaswamy H. Sarma.

Theoretical investigation of the atmospheric implication for the reaction of •OH radical with CF2C(CH3)-CX3, X = H, F.

The atmospheric implication of the hydrofluoroolefines (HFO) CF2C(CH3)-CX3, X=(H,F), through the reactions with •OH radical were assessed using the M06-2X/6-311++G(df,p)//6-31+G(df,p) method. The rate coefficient was calculated over the temperature range 200-500 K, and was accurately expressed in non-Arrhenius form exp(a+bT-1+cT-2) cm3molecule-1s-1, where a, b, and c are real constants. This served to estimate the atmospheric lifetime along with the photochemical ozone creation potential (POCP), which yielded lifetimes of 0.39 and 3.53 days and POCPs of 51.00 and 3.57 for X = H and F, respectively. The radiative forcing efficiencies (RFEs) were also estimated at G96LYP/6-311G(df,p) along with the global warming potentials (GWPs). The results showed negligible impact towards global warming for the HFOs.

Characterization of engine lubricants by fluorescence spectroscopy and chemometrics.

In this study, principal component analysis (PCA) and parallel factor analysis (PARAFAC) combined with excitation-emission matrix fluorescence (EEMF) were used to determine the most efficient excitation wavelengths of engine lubricants; identify their fluorophores; classify them and look for correlations between their fluorescence and their physical parameters. EEMF spectra were obtained for the different samples in the range of 260 to 600 nm, and 300 to 700 nm for excitation and emission wavelengths respectively. PCA and PARAFAC showed that the efficient excitation wavelengths for engine lubricants are 300, 350, 400, 450 and 470 nm. These five wavelengths represented the maxima of the PARAFAC recovered excitation profiles, of which two were attributed to fluorene and pyrene. The relative proportions of the PARAFAC retrieved components were used to classify engine lubricants with a satisfactory percentage of classification of 70%. Finally, a good correlation was obtained between some physical parameters (particularly the viscosity) of engine lubricants and their fluorescence.

Temperature-dependent oxidation of BSCAPE molecule in methanol medium.

Temperature-dependent solvation free energy and oxidation by free energy of ionization of 2-Phenylethyl (2E)-3-(1-benzenesulfonyl-4,5-dihydroxyphenyl) acrylate (BSCAPE) in methanol medium are the concerns of the present work. This molecule is a relevant phenolic acid enclosing multiple bioactivities. The explicit, implicit and discrete-continuum models of solvation were used. The methanol molecules were coordinated to this acid to form cluster complexes. The dual method M06-2X/6-31++G(d,p)//B3LYP/6-31G(d) was employed along with basis set superposition error correction. The results show that, the free energy of coordination and solvation are distant. Both quantities increase with temperature. From discrete-continuum treatment, there is non-spontaneity of solvation process, while coordination yielded spontaneity and non-spontaneity at cold and hot room temperatures, respectively. The ionization potential in gas phase, decreases with temperature. All the solvation models yielded lower ionization potential than that of gas phase. Thus, it follows that, the increase of temperature and methanol medium favours the oxidation of BSCAPE. Consequently, this favours its metabolism processes.

Insight of UV-vis spectra and atmospheric implication for the reaction of ˙OH radical towards glyphosate herbicide and its hydrates.

The rate constant of the reactions of ˙OH radicals with glyphosate (GPS) and its hydrates (GPS(H2O) n=1-3) were evaluated using the dual method M06-2X/6-311++G(df,p)//6-31+G(df,p) over the temperature range of 200-400 K. The results served to estimate the atmospheric lifetime along with the photochemical ozone creation potential (POCP). The calculations yielded an atmospheric lifetime of 2.34 hours and a POCP of 24.7 for GPS. Upon addition of water molecules, there is an increase of lifetime and decrease of POCP for water monomer and water dimer. The POCP for water trimer is slightly above the gaseous GPS. However, the POCPs of GPS and its hydrates are comparable to that of alkanes. The GPS and its hydrates were found to be a potential reservoir of CO2. The acidification potential (AP) of GPS was found to be 0.189 and decreases upon addition of water molecules. This shows negligible contribution to rain acidification as the AP is less than that of SO2. The UV-vis spectra were attained using the M06-L/6-311++G(3df,3pd) method and cover the range 160-260 nm which fits well with experiment.

Infrared spectra of PEHA molecule and its resistance to oxidation in water and methanol media at 298.15 K: solvent cluster size dependency.

The present work investigates the infrared spectra and solvation free energies (SE) of PEHA ((E)-2-(Pyridin-2-yl) ethyl 3-(3,4-dihydroxyphenyl) acrylate) and their impact on the oxidation. The latter was examined through the ionization potential parameter (IP). These investigations were carried out by the DFT method at B3LYP/6-31G(d) for optimization and frequency calculations and corrected for BSSE. X3LYP/6-311++G(2d,2p) was employed for single-point energy calculations. Water and methanol cluster sizes were used for solvation through the explicit solvent model. Thus, the infrared spectra show that the overview frequencies of PEHA compare well with the experimental results. The intense infrared absorptions of complexes are due to the stretching of O-H bonds of solvent clusters in the range 2600-3850 cm-1. The binding energy per solvent molecule of complexes was calculated and shows that water and methanol clusters mimic the liquid state as from 5 to 10 solvent molecules. The SE of PEHA increases with the increase of the cluster size of water and methanol in the direction of the limit. The latter was censured by the solvation done using the combined explicit-implicit solvent model. As for IP parameter, the results are largely above the IP limit and lower than the IP from gas phase. Thus, water and methanol media have an effect of lowering the IP of PEHA compound. Consequently, both media favour the oxidation of PEHA molecule, which facilitates its metabolism in human organism.

Effects of counterions and solvents on the geometrical and vibrational features of dinucleoside-monophosphate (dNMP): case of 3',5'-dideoxycytidine-monophosphate (dDCMP).

The effects of the interaction of the monovalent (Li+, Na+, K+) and divalent (Mg2+) counterions hexahydrated (6H2O), with the PO2- group, on the geometrical and vibrational characteristics of 3', 5'-dDCMP, were studied using the DFT/B3LYP/6-31++G(d) method. These calculations were performed using the explicit (6H2O) and hybrid (6H2O/Continuum) solvation models. The optimizations reveal that in the conformation g-g- and in the explicit model of solvation, the small ions (Li+, Na+) deviate from the bisector plane of the angle O1-P-O2 and the large ions (K+ and Mg2+) remain in this plane, whereas in the hybrid model of solvation, the counterions deviate from this plane. However, when the conformer is g+g+, the monovalent counterions deviate and divide the remainder of the plane regardless of the type of solvation model. In addition, the g-g- conformer is the most stable in the presence of the explicit solvent, while the g+g+ conformer is the most stable in the presence of the hybrid solvent. Finally, the normal modes of the conformers g-g- and g+g+ in the presence of the counterions in the hybrid model show a better agreement with the available experimental data of the DNA forms A, B (g-g-), and Z (g+g+) relatively to the explicit model. This very good agreement is illustrated by the very small deviations ≤ 0.08% (g-g-) and ≤ 0.41% (g+g+) observed between the calculated and experimental data for the PO2- (asymmetric) stretching mode in the presence of the counterion K+ in the hybrid model. Graphical abstract.

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.

DFT Study of Photochemical Properties and Radiative Forcing Efficiency Features of the Stereoisomers cis- and trans-CHCl═CH-CF3.

The accurate assessment of radiative forcing efficiency (RFE) of a greenhouse gas is based on the precise knowledge of its structure and infrared absorption spectrum. The present work investigates the UV-vis absorption spectra and IR absorption spectra that are used for the determination of RFE of the short-lived compounds, cis- and trans-CHCl═CHCF3 (CTFP). These investigations were carried out with six different density functional theory (DFT) methods B3LYP, CAM-B3LYP, M06, M06-2X, TPSS0, and ωB97X-D associated to the basis set 6-31G(3df). Therefrom, the relative populations of the two states cis and trans for temperatures over the range 220-370 K at 1 atm and along the atmospheric altitude were assessed. It turns out that trans-CTFP is the abundant component between the two states. This review reveals that B3LYP and M06 reproduce well the experimental results of UV-vis spectra of trans-CTFP. As for cis-CTFP, EOM-CCSD is not well fitted by DFT methods. The cis- to trans-CTFP isomerization leads to the red shift for DFT methods and to the blue shift in regard to EOM-CCSD and experimental results. The IR absorption spectra are well fitted by B3LYP over the range 500-1600 cm-1 and TPSS0 over 1300-2000 cm-1 for both stereoisomers. Moreover, the root-mean-square errors (RMSEs) of frequencies from experimental data are lower for B3LYP and TPSS0 for both systems. The computed IR absorption band strengths over 500-2000 cm-1 for cis- and over 600-1800 cm-1 for trans-CTFP are consistent with the experiment. The relevant descriptor RFEs of the climate effect were calculated using a narrow band model for a constant vertical profile and then corrected with a lifetime factor for different computational methods. The computed values correlate well with the experimental results for both stereoisomers except M06-2X and TPSS0. It is worth noting that, for both systems, the intense radiative forcing spectra are located at frequencies ranging in 1000-1200 cm-1. The lower forcings of trans-CTFP lying in the atmospheric window region 800-1000 cm-1 are greater than those of cis-CTFP. Therefore, RFE(trans-CTFP) = 1.127 RFE(cis-CTFP).

Thermodynamic of solvation, solute - Solvent electron transfer and ionization potential of BSCAPE molecule and its UV-vis spectra in aqueous solution.

The molecular system 2-Phenylethyl (2E)-3-(1-benzenesulfonyl-4,5-dihydroxyphenyl) acrylate (BSCAPE) is a phenolic acid that covers a large spectrum of biological properties. The investigations of solvation and oxidation processes of BSCAPE molecule by computational means were the challenge of this present work. Water was required for solvation throughout the work. The explicit H2O were sequentially added to form the complexes BSCAPE(H2O)n=0-11. The discrete - continuum model was at the heart of this work. DFT and TD-DFT both associated to the continuum model SMD were required. Hence, the structures, the solvation energies, the energies of solute - solvent electron transfer (SSET), the ionisation potential (IP), and the UV-vis spectra were studied. It comes out that, the structure of the CAPE part included in BSCAPE agrees well with the available experimental values of CAPE but with a minor influence due to the presence of benzensulfonyl group. The enthalpy and free energy of solvation increase linearly with nH2O. The global reactivity indexes were assessed to appreciate the oxidation of BSCAPE. The latter quality was strongly assessed by the enthalpy and free energy of SSET and IP. The SSET potential increase with nH2O and the size of water clusters. The values 723.16 and 711.62 kJ/mol were found for enthalpy and free energy of IP respectively. Then in aqueous solution, the results fall down and upon addition of nH2O, they approach gas phase value for 11H2O and still are not stabilized. Therefore, the resistance to oxidation starts to raise at this level. Elsewhere, the UV-vis spectra of BSCAPE present four important peaks about 279.3, 234.8, 208.4 and 199.4 nm in gaseous state. The excitation shifts to the red as the number of H2O increase. Their oscillator strengths also increase with solvation.

Hydration of l-glycylvaline and l-glycylvalylglycine zwitterions: Structural and vibrational studies using DFT method.

Solvent effects on the structural and vibrational features of l-glycylvaline (L-GV) and l-glycylvalylglycine (L-GVG) in zwitterionic forms have been performed by means of DFT method. Relaxed potential energy surface scans (RPES) performed at B3LYP/6-31++G(d) level were used to map the reaction coordinate surfaces and to identify the geometries corresponding to the minima energy. Explicit solvation model, where L-GV and L-GVG are respectively surrounded by 9 and 11 water molecules interacting with H-donor and H-acceptor sites, as well as the different hybrid solvation models of solvation (explicit/COSMO, explicit/PCM and explicit/CPCM) allowed to analyze the hydration effects. Those number of water molecules are sufficient to fully hydrate carboxyl(CtOO-), amine (NtH3+) and amide (NH, C=O) groups. Harmonic vibrational modes calculated after geometry optimization on each solvated complex are performed at B3LYP/6-31++g(d) and PBE0/6-31++g(d) methods and a post-processing treatment enable us to assign the vibrational modes of LGV and L-GVG. The frequencies of the assigned modes obtained using B3LYP in explicit/COSMO are in good agreement with available IR and Raman values than those found in both explicit/PCM and explicit/CPCM which proved to be very close.

DFT study of geometrical and vibrational features of a 3',5'-deoxydisugar-monophosphate (dDSMP) DNA model in the presence of counterions and solvent.

The B3LYP/6-31++G* theoretical level was used to study the influence of various hexahydrated monovalent (Li+, Na+, K+) and divalent (Mg2+) metal counterions in interaction with the charged PO2- group, on the geometrical and vibrational characteristics of the DNA fragments of 3',5'-dDSMP, represented by four conformers (g+g+, g+t, g-g- and g-t). All complexes were optimized through two solvation models [the explicit model (6H2O) and the hybrid model (6H2O/Continuum)]. The results obtained established that, in the hybrid model, counterions (Li+, Na+, K+, Mg2+) always remain in the bisector plane of the O1-P-O2 angle. When these counterions are explicitly hydrated, the smallest counterions (Li+, Na+) deviate from the bisector plane, while the largest counterions (K+ and Mg2+) always remain in the same plane. On the other hand, the present calculations reveal that the g+g+ conformer is the most stable in the presence of monovalent counterions, while conformers g+t and g-t are the most stable in the presence of the divalent counterion Mg2+. Finally, the hybrid solvation model seems to be in better agreement with the available crystallographic and spectroscopic (Raman) experiments than the explicit model. Indeed, the six conformational torsions of the C4'-C3'-O3'-PO-2-O5'-C5'-C4' segment of all complexes of the g-g- conformer in 6H2O/Continuum remain similar to the available experimental data of A- and B-DNA forms. The calculated wavenumbers of the g+g+ conformer in the presence of the monovalent counterion and of g-t conformer in presence of the divalent counterion in the hybrid model are in good agreement with the Raman experimental data of A- and B-DNA forms. In addition, the maximum deviation between the calculated wavenumbers in the 6H2O/Continuum for the g+g+ conformer and experimental value measured in an aqueous solution of the DMP-Na+ complex, is <1.07% for the PO2- (asymmetric and symmetric) stretching modes and <2.03% for the O5'-C5' and O3'-C3' stretching modes. Graphical abstract dDSMP-(OO)- Mg2+/6W/Continuum.

Structure, antioxidative potency and potential scavenging of OH and OOH of phenylethyl-3,4-dihydroxyhydrocinnamate in protic and aprotic media: DFT study.

DFT methods including B3LYP, B3PW91 and M05-2x associated to 6-31+G(d,p) were used for the structural and antioxidant potency studies of phenylethyl-3,4-dihydroxy-hydrocinnamate (PDH). Solvents were employed according to their protric and aprotic character. So, calculated structures agree with the experimental data. O4H4 is propitious to scavenge radicals whatever the medium except in water where O3H3 and O4H4 are competitive. The explicit solvents of dichloromethane (DCM) and water present a disparity of OH bond dissociation enthalpy and free energy (BDE and BDFE). These parameters are low in continuum except in water. The ionization potentials (IP) and potential affinities (PA) are low in solvents. BDE, IP and PA are each, approximatively constant in mixed solvent treatment in water using n-H2O (n=3,5,8). Elsewhere, H-atom transfer (HAT) mechanism is favoured in vacuum and DCM, whereas sequential proton loss electron transfer (SPLET) is likely in protic solvents. A discord between HAT and SPLET in benzene is observed. The PDH compound is more antioxidant and resistant to oxidation than caffeic acid phenethyl ester (CAPE). The potential of scavenging of OH and OOH whatever the reaction channel shows that they decay rapidly in any media through HAT. PDH is easily deprotonated in the protic solvents and the resulting product is the most antioxidant and the least resistant to oxidation.

Solvent effects on the structures and vibrational features of zwitterionic dipeptides: L-diglycine and L-dialanine.

Calculations were done by applying the B3LYP/6-31++G(d) method on the zwitterionic L-diglycine and L-dialanine to study the solvent effects on their structures and vibrational features. Three models of solvation (implicit, explicit, and explicit in implicit) were used and the subsequent resulting values compared. Even though both dipeptides surrounded by 12 water molecules seem sufficient to stabilize their zwitterionic characters, notably to avoid the proton transfer between the backbone (N t H[Formula: see text], COO (-)) groups, the hybrid model of solvation (explicit in implicit noted 12W/Continuum) appears to be in better agreement with available IR and Raman experiments than explicit and implicit models. The harmonic vibrational modes derived from geometry optimization of L-diglycine and L-dialanine in 12W/Continuum, agree with the available IR and Raman experimental values within 1 % for L-diglycine and 2 % for L-dialanine, and they appear more accurate than those found using the explicit model (12W). Graphical Abstract DFT/6-31++G∗ Optimized structures of L-diglycine (top) and L-dialanine (bottom) surrounded by 12 water molecules all embedded in a continuum.

DFT study of the effect of solvent on the H-atom transfer involved in the scavenging of the free radicals (·)HO2 and (·)O2(-) by caffeic acid phenethyl ester and some of its derivatives.

H-atom transfer from caffeic acid phenethyl ester (CAPE), MBC (3-methyl-2-butenyl caffeate), BC (benzoic caffeate), P3HC (phenethyl-3-hydroxycinnamate), and P4HC (phenethyl-4-hydroxycinnamate) to the selected free radicals (·)HO2 and (·)O2(-) was studied. Such a transfer can proceed in three different ways: concerted proton-coupled electron transfer (CPCET), electron transfer followed by proton transfer (ET-PT), and proton transfer followed by electron transfer (PT-ET). The latter pathway is sometimes competitive with SPLET (sequential proton loss electron transfer) in polar media. Analyzing the thermodynamic descriptors of the reactions of CAPE and its derivatives with co-reactive species-in particular, the free energies of reactions, the activation barrier to the CPCET mechanism, and their rate constants-appears to be the most realistic method of investigating the H-atom transfers of interest. These analyses were performed via DFT calculations, which agree well with the data acquired from experimental studies (IC50) and from CBS calculations. The CPCM solvation model was used throughout the work, while the SMD model-employed as a reference-was used only for CAPE. The main conclusion drawn from the analysis was that SPLET is the mechanism that governs the reaction of phenolic acids with (·)HO2, while PT-ET governs the reaction of phenols with (·)O2(-). In kinetic investigations of the CPCET process, the rate constant decreases as the solvent polarity increases, so the reaction velocity slows down.

Revision of the thermodynamics of the proton in gas phase.

Proton transfer is ubiquitous in various physical/chemical processes, and the accurate determination of the thermodynamic parameters of the proton in the gas phase is useful for understanding and describing such reactions. However, the thermodynamic parameters of such a proton are usually determined by assuming the proton as a classical particle whatever the temperature. The reason for such an assumption is that the entropy of the quantum proton is not always soluble analytically at all temperatures. Thereby, we addressed this matter using a robust and reliable self-consistent iterative procedure based on the Fermi-Dirac formalism. As a result, the free proton gas can be assumed to be classical for temperatures higher than 200 K. However, it is worth mentioning that quantum effects on the gas phase proton motion are really significant at low temperatures (T ≤ 120 K). Although the proton behaves as a classical particle at high temperatures, we strongly recommend the use of quantum results at all temperatures, for the integrated heat capacity and the Gibbs free energy change. Therefore, on the basis of the thermochemical convention that ignores the proton spin, we recommend the following revised values for the integrated heat capacity and the Gibbs free energy change of the proton in gas phase and, at the standard pressure (1 bar): ΔH0→T = 6.1398 kJ mol(-1) and ΔG0→T = -26.3424 kJ mol(-1). Finally, it is important noting that the little change of the pressure from 1 bar to 1 atm affects notably the entropy and the Gibbs free energy change of the proton.

Excitation-emission matrix fluorescence coupled to chemometrics for the exploration of essential oils.

Excitation-emission matrix fluorescence (EEMF) coupled to chemometrics was used to explore essential oils (EOs). The spectrofluorometer was designed with basic and inexpensive materials and was accompanied by appropriate tools for data pre-treatment. Excitation wavelengths varied between 320 nm and 600 nm while emission wavelengths were from 340 nm to 700 nm. Excitation-emission matrix (EEM) spectra of EOs presented different features, revealing the presence of varying fluorophores. EOs from the same species but from different origins presented almost the same spectra, showing the possibility that EEM spectra could be used as additional parameters in the standardisation of EOs. With the aid of unfold principal component analysis (UPCA), resemblances obtained by spectral analysis of EOs were confirmed. A five components parallel factor analysis (PARAFAC) model was used to find the profiles of fluorophores in EOs. One of those components was associated to chlorophyll a.

Structures of protonated methanol clusters and temperature effects.

The accurate evaluation of pKa's, or solvation energies of the proton in methanol at a given temperature is subject to the determination of the most favored structures of various isomers of protonated (H(+)(MeOH)n) and neutral ((MeOH)n) methanol clusters in the gas phase and in methanol at that temperature. Solvation energies of the proton in a given medium, at a given temperature may help in the determination of proton affinities and proton dissociation energies related to the deprotonation process in that medium and at that temperature. pKa's are related to numerous properties of drugs. In this work, we were interested in the determination of the most favored structures of various isomers of protonated methanol clusters in the gas phase and in methanol, at a given temperature. For this aim, the M062X/6-31++G(d,p) and B3LYP/6-31++G(d,p) levels of theory were used to perform geometries optimizations and frequency calculations on various isomers of (H(+)(MeOH)n) in both phases. Thermal effects were retrieved using our homemade FORTRAN code. Thus, we accessed the relative populations of various isomers of protonated methanol clusters, in both phases for temperatures ranging from 0 to 400 K. As results, in the gas phase, linear structures are entropically more favorable at high temperatures, while more compact ones are energetically more favorable at lower temperatures. The trend is somewhat different when bulk effects are taken into account. At high temperatures, the linear structure only dominates the population for n ≤ 6, while it is dominated by the cyclic structure for larger cluster sizes. At lower temperatures, compact structures still dominate the population, but with an order different from the one established in the gas phase. Hence, temperature effects dominate solvent effects in small cluster sizes (n ≤ 6), while the reverse trend is noted for larger cluster sizes.

Solvation Energies of the Proton in Methanol.

pKa's, proton affinities, and proton dissociation free energies characterize numerous properties of drugs and the antioxidant activity of some chemical compounds. Even with a higher computational level of theory, the uncertainty in the proton solvation free energy limits the accuracy of these parameters. We investigated the thermochemistry of the solvation of the proton in methanol within the cluster-continuum model. The scheme used involves up to nine explicit methanol molecules, using the IEF-PCM and the strategy based on thermodynamic cycles. All computations were performed at B3LYP/6-31++G(dp) and M062X/6-31++G(dp) levels of theory. It comes out from our calculations that the functional M062X is better than B3LYP, on the evaluation of gas phase clustering energies of protonated methanol clusters, per methanol stabilization of neutral methanol clusters and solvation energies of the proton in methanol. The solvation free energy and enthalpy of the proton in methanol were obtained after converging the partial solvation free energy of the proton in methanol and the clustering free energy of protonated methanol clusters, as the cluster size increases. Finally, the recommended values for the solvation free energy and enthalpy of the proton in methanol are -257 and -252 kcal/mol, respectively.