Electronic Currents Induced by Optical Fields and Rotatory Power Density in Chiral Molecules

The electric dipole–magnetic dipole polarizability tensor κ′, introduced to interpret the optical activity of chiral molecules, has been expressed in terms of a series of density functions kαβ′, which can be integrated all over the three-dimensional space to evaluate components καβ′ and trace καα′. A computational approach to kαβ′, based on frequency-dependent electronic current densities induced by monochromatic light shining on a probe molecule, has been developed. The dependence of kαβ′ on the origin of the coordinate system has been investigated in connection with the corresponding change of καβ′. It is shown that only the trace kαα′ of the density function defined via dynamic current density evaluated using the continuous translation of the origin of the coordinate system is invariant of the origin. Accordingly, this function is recommended as a tool that is quite useful for determining the molecular domains that determine optical activity to a major extent. A series of computations on the hydrogen peroxide molecule, for a number of different HO–OH dihedral angles, is shown to provide a pictorial documentation of the proposed method.     

Non-Peptide Opioids Differ in Effects on Mu-Opioid (MOP) and Serotonin 1A (5-HT1A) Receptors Heterodimerization and Cellular Effectors (Ca2+, ERK1/2 and p38) Activation

The importance of the dynamic interplay between the opioid and the serotonin neuromodulatory systems in chronic pain is well recognized. In this study, we investigated whether these two signalling pathways can be integrated at the single-cell level via direct interactions between the mu-opioid (MOP) and the serotonin 1A (5-HT_1A) receptors. Using fluorescence cross-correlation spectroscopy (FCCS), a quantitative method with single-molecule sensitivity, we characterized in live cells MOP and 5-HT_1A interactions and the effects of prolonged (18 h) exposure to selected non-peptide opioids: morphine, codeine, oxycodone and fentanyl, on the extent of these interactions. The results indicate that in the plasma membrane, MOP and 5-HT_1A receptors form heterodimers that are characterized with an apparent dissociation constant Kdapp = (440 ± 70) nM). Prolonged exposure to all non-peptide opioids tested facilitated MOP and 5-HT_1A heterodimerization and stabilized the heterodimer complexes, albeit to a different extent: Kd, Fentanylapp = (80 ± 70) nM), Kd,Morphineapp = (200 ± 70) nM, Kd, Codeineapp = (100 ± 70) nM and Kd, Oxycodoneapp = (200 ± 70) nM. The non-peptide opioids differed also in the extent to which they affected the mitogen-activated protein kinases (MAPKs) p38 and the extracellular signal-regulated kinase (Erk1/2), with morphine, codeine and fentanyl activating both pathways, whereas oxycodone activated p38 but not ERK1/2. Acute stimulation with different non-peptide opioids differently affected the intracellular Ca²⁺ levels and signalling dynamics. Hypothetically, targeting MOP–5-HT_1A heterodimer formation could become a new strategy to counteract opioid induced hyperalgesia and help to preserve the analgesic effects of opioids in chronic pain.     

Removal of Carbamazepine in Aqueous Solution by CoS2/Fe2+/PMS Process

Carbamazepine (CBZ), as a typical pharmaceutical and personal care product (PPCP), cannot be efficiently removed by the conventional drinking water and wastewater treatment process. In this work, the CoS₂/Fe²⁺/PMS process was applied for efficient elimination of CBZ. The CBZ removal efficiency of CoS₂/Fe²⁺/PMS was 2.5 times and 23 times higher than that of CoS₂/PMS and Fe²⁺/PMS, respectively. The intensity of DMPO-HO• and DMPO-SO4•− followed the order of Fe²⁺/PMS < CoS₂/PMS < CoS₂/Fe²⁺/PMS, also suggesting the CoS₂/Fe²⁺/PMS process has the highest oxidation activity. The effects of reaction conditions (e.g., CoS₂ dosage, Fe²⁺ concentration, PMS concentration, initial CBZ concentration, pH, temperature) and water quality parameters (e.g., SO42−, NO3−, H2PO4−, Cl−, NH4+, humic acid) on the degradation of CBZ were also studied. Response surface methodology analysis was carried out to obtain the best conditions for the removal of CBZ, which are: Fe²⁺ = 70 µmol/L, PMS = 240 µmol/L, CoS₂ = 0.59 g/L. The sustainability test demonstrated that the repeated use of CoS₂ for 8 successive cycles resulted in little function decrease (<10%). These findings suggest that CoS₂/Fe²⁺/PMS may be a promising method for advanced treatment of tailwater from sewage treatment plant.     

Interaction Energy Analysis of Monovalent Inorganic Anions in Bulk Water Versus Air/Water Interface

Soft anions exhibit surface activity at the air/water interface that can be probed using surface-sensitive vibrational spectroscopy, but the structural implications of this surface activity remain a matter of debate. Here, we examine the nature of anion–water interactions at the air/water interface using a combination of molecular dynamics simulations and quantum-mechanical energy decomposition analysis based on symmetry-adapted perturbation theory. Results are presented for a set of monovalent anions, including Cl⁻, Br⁻, I⁻, CN⁻, OCN⁻, SCN⁻, NO2−, NO3−, and ClOn− (n=1,2,3,4), several of which are archetypal examples of surface-active species. In all cases, we find that average anion–water interaction energies are systematically larger in bulk water although the difference (with respect to the same quantity computed in the interfacial environment) is well within the magnitude of the instantaneous fluctuations. Specifically for the surface-active species Br⁻(aq), I⁻(aq), ClO4−(aq), and SCN⁻(aq), and also for ClO⁻(aq), the charge-transfer (CT) energy is found to be larger at the interface than it is in bulk water, by an amount that is greater than the standard deviation of the fluctuations. The Cl⁻(aq) ion has a slightly larger CT energy at the interface, but NO3−(aq) does not; these two species are borderline cases where consensus is lacking regarding their surface activity. However, CT stabilization amounts to <20% of the total induction energy for each of the ions considered here, and CT-free polarization energies are systematically larger in bulk water in all cases. As such, the role of these effects in the surface activity of soft anions remains unclear. This analysis complements our recent work suggesting that the short-range solvation structure around these ions is scarcely different at the air/water interface from what it is in bulk water. Together, these observations suggest that changes in first-shell hydration structure around soft anions cannot explain observed surface activities.     

The Relationship between the IC50 Values and the Apparent Inhibition Constant in the Study of Inhibitors of Tyrosinase Diphenolase Activity Helps Confirm the Mechanism of Inhibition

Tyrosinase is the enzyme involved in melanization and is also responsible for the browning of fruits and vegetables. Control of its activity can be carried out using inhibitors, which is interesting in terms of quantitatively understanding the action of these regulators. In the study of the inhibition of the diphenolase activity of tyrosinase, it is intriguing to know the strength and type of inhibition. The strength is indicated by the value of the inhibition constant(s), and the type can be, in a first approximation: competitive, non-competitive, uncompetitive and mixed. In this work, it is proposed to calculate the degree of inhibition (iD), varying the concentration of inhibitor to a fixed concentration of substrate, L-dopa (D). The non-linear regression adjustment of iD with respect to the initial inhibitor concentration [I]0 allows for the calculation of the inhibitor concentration necessary to inhibit the activity by 50%, at a given substrate concentration (IC₅₀), thus avoiding making interpolations between different values of iD. The analytical expression of the IC₅₀, for the different types of inhibition, are related to the apparent inhibition constant (KIapp). Therefore, this parameter can be used: (a) To classify a series of inhibitors of an enzyme by their power. Determining these values at a fixed substrate concentration, the lower IC₅₀, the more potent the inhibitor. (b) Checking an inhibitor for which the type and the inhibition constant have been determined (using the usual methods), must confirm the IC₅₀ value according to the corresponding analytical expression. (c) The type and strength of an inhibitor can be analysed from the study of the variation in iD and IC₅₀ with substrate concentration. The dependence of IC₅₀ on the substrate concentration allows us to distinguish between non-competitive inhibition (iD does not depend on [D]0) and the rest. In the case of competitive inhibition, this dependence of iD on [D]0 leads to an ambiguity between competitive inhibition and type 1 mixed inhibition. This is solved by adjusting the data to the possible equations; in the case of a competitive inhibitor, the calculation of KI1app is carried out from the IC₅₀ expression. The same occurs with uncompetitive inhibition and type 2 mixed inhibition. The representation of iD vs. n, with n=[D]0/KmD, allows us to distinguish between them. A hyperbolic iD vs. n representation that passes through the origin of coordinates is a characteristic of uncompetitive inhibition; the calculation of KI2app is immediate from the IC₅₀ value. In the case of mixed inhibitors, the values of the apparent inhibition constant of meta-tyrosinase (Em) and oxy-tyrosinase (Eox), KI1app and the apparent inhibition constant of metatyrosinase/Dopa complexes (EmD) and oxytyrosinase/Dopa (EoxD), KI2app are obtained from the dependence of iD vs. n, and the results obtained must comply with the IC₅₀ value.     

Deuterium Isotope Effects on Acid-Base Equilibrium of Organic Compounds

Deuterium isotope effects on acid–base equilibrium have been investigated using a combined path integral and free-energy perturbation simulation method. To understand the origin of the linear free-energy relationship of ΔpKa=pKaD2O−pKaH2O versus pKaH2O, we examined two theoretical models for computing the deuterium isotope effects. In Model 1, only the intrinsic isotope exchange effect of the acid itself in water was included by replacing the titratable protons with deuterons. Here, the dominant contribution is due to the difference in zero-point energy between the two isotopologues. In Model 2, the medium isotope effects are considered, in which the free energy change as a result of replacing H₂O by D₂O in solute–solvent hydrogen-bonding complexes is determined. Although the average ΔpKa change from Model 1 was found to be in reasonable agreement with the experimental average result, the pKaH2O dependence of the solvent isotope effects is absent. A linear free-energy relationship is obtained by including the medium effect in Model 2, and the main factor is due to solvent isotope effects in the anion–water complexes. The present study highlights the significant roles of both the intrinsic isotope exchange effect and the medium solvent isotope effect.     

Explorations on Thermodynamic and Kinetic Performances of Various Cationic Exchange Durations for Synthetic Clinoptilolite

Various cation–exchanged clinoptilolites (M–CPs, M = Li⁺, Cs⁺, Ca²⁺, Sr²⁺) were prepared, and their exchanged thermodynamic (and kinetic) properties and adsorption performances for CH₄, N₂, and CO₂ were investigated. The results demonstrated that the relative crystallinity of M–CP_S decreased with the increase of exchange times. Their chemisorbed water weight loss gradually increased with the increasing exchange times, except that of Cs–x–CP. The Δ_rGmθ values of exchange process of Li⁺, Cs⁺, Ca²⁺, or Sr² presented the increased trend with the enhanced exchange times, but they decreased as the temperature increased. The negative Δ_rGmθ values and the positive Δ_rHmθ and Δ_rSmθ values suggested that the exchanged procedure belonged to spontaneous, endothermic, and entropy-increasing behaviors; their kinetic performances followed a pseudo–second–order model. However, the calculated E_a values of exchange process showed the increased tendencies with the enhanced exchange times, indicating that the exchange process became more difficult. Finally, the preliminary adsorption results indicated that the maximum adsorption amount at 273 K and 1 bar was 0.51 mmol/g of CH₄ and 0.38 mmol/g of N₂ by (Na, K)–CP, and 2.32 mmol/g of CO₂ by Li–6–CP.     

Studies of the Formation of Inclusion Complexes Derivatives of Cinnamon Acid with α-Cyclodextrin in a Wide Range of Temperatures Using Conductometric Methods

The electrical conductivities of aqueous solutions of sodium salts of trans-4-hydroxycinnamic acid (trans-p-coumaric acid), trans-3,4-dihydroxycinnamic acid (trans-caffeic acid), trans-4-hydroxy-3-methoxycinnamic acid, (trans-ferulic acid) and trans-3-phenylacrylic acid (trans-cinnamic acid) with α-cyclodextrin were measured in the temperature range of 288.15 K–318.15 K. For the first time in the literature, using the limiting molar conductivity (Λmo) obtained from conductivity measurements, the values of the complexation constants (K_f) of the salts of phenolic acid derivatives with α-cyclodextrin were determined using a modified low concentration chemical model (IcCM). An attempt was also made to analyze the individual thermodynamic functions ΔGo, ΔHo and ΔSo describing the complexation process as a function of temperature changes. The obtained results show that the process of formation of inclusion complexes is exothermic and is spontaneous.     

Identification of Stingless Bee Honey Adulteration Using Visible-Near Infrared Spectroscopy Combined with Aquaphotomics

Honey is a natural product that is considered globally one of the most widely important foods. Various studies on authenticity detection of honey have been fulfilled using visible and near-infrared (Vis-NIR) spectroscopy techniques. However, there are limited studies on stingless bee honey (SBH) despite the increase of market demand for this food product. The objective of this work was to present the potential of Vis-NIR absorbance spectroscopy for profiling, classifying, and quantifying the adulterated SBH. The SBH sample was mixed with various percentages (10–90%) of adulterants, including distilled water, apple cider vinegar, and high fructose syrup. The results showed that the region at 400–1100 nm that is related to the color and water properties of the samples was effective to discriminate and quantify the adulterated SBH. By applying the principal component analysis (PCA) on adulterants and honey samples, the PCA score plot revealed the classification of the adulterants and adulterated SBHs. A partial least squares regression (PLSR) model was developed to quantify the contamination level in the SBH samples. The general PLSR model with the highest coefficient of determination and lowest root means square error of cross-validation (RCV2=0.96 and RMSECV=5.88 %) was acquired. The aquaphotomics analysis of adulteration in SBH with the three adulterants utilizing the short-wavelength NIR region (800–1100 nm) was presented. The structural changes of SBH due to adulteration were described in terms of the changes in the water molecular matrix, and the aquagrams were used to visualize the results. It was revealed that the integration of NIR spectroscopy with aquaphotomics could be used to detect the water molecular structures in the adulterated SBH.