Mechanism, selectivity promotion, and new ultraselective pathways in Ag-catalyzed heterogeneous epoxidation

The selective oxidation of styrene on clean and modified Ag(100) surfaces has been studied by synchrotron fast XPS and temperature-programmed reaction spectroscopy. By following the time dependence of surface species, it is unequivocally demonstrated that the necessary and sufficient conditions for epoxide formation are oxygen adatoms and pi-adsorbed alkene molecules. Increased oxygen coverage and coadsorbed Cs have pronounced and opposite effects on epoxidation selectivity, consistent with the view that the valence charge density on O(a) is pivotal in determining this property. Submonolayer quantities of Cs nitrate generated in situ open a new, low-temperature ultraselective, epoxidation pathway thought to involve direct oxygen transfer from the oxyanion to the alkene.     

Biological Activities of Organic Extracts of the Genus Aristolochia: A Review from 2005 to 2021

Different ethnomedicinal studies have investigated the relationship between various phytochemicals as well as organic extracts and their bioactive aspects. Studies on biological effects are attributed to secondary metabolites such as alkaloids, phenolic compounds, and terpenes. Since there have been no reviews in the literature on the traditional, phytochemical, and ethnomedicinal uses of the genus Aristolochia so far, this article systematically reviews 141 published studies that analyze the associations between secondary metabolites present in organic extracts and their beneficial effects. Most studies found associations between individual secondary metabolites and beneficial effects such as anticancer activity, antibacterial, antioxidant activity, snake anti-venom and anti-inflammatory activity. The aim of this review was to analyze studies carried out in the period 2005–2021 to update the existing knowledge on different species of the genus Aristolochia for ethnomedicinal uses, as well as pharmacological aspects and therapeutic uses.     

Synthesis and characterization of [Cp*Fe-dicyclopenta(a,f)naphthalene-FeCp*] and [Cp*Fe-dicyclopenta(a,f)naphthalene-FeCp*] BF4

[Cp*Fe-dicyclopenta(a,f)naphthalene-FeCp*]ⁿ⁺ (Cp*=pentamethylciclopentadiene, n=0, 1), respectively named complexes V and VI, were synthesized and characterized. The X-ray structure has been solved and ¹H-, ¹³C-NMR and elemental analysis were performed for the n=0 complex. Cyclic voltammetry showed a potential difference of 360 mV within the two redox peaks. An absorption band at 850 nm was assigned to an intervalence band. The Mössbauer investigations show a uniform Fe²⁺ environment for the neutral compound and two sites, assigned to Fe²⁺ and Fe³⁺ for the monoxidized compound. The information gathered by all the previously mentioned techniques indicates that the studied binuclear compound belongs to the mixed valence class II using Robin and Day classification.     

Full-Atom Model of the Agonist LPS-Bound Toll-like Receptor 4 Dimer in a Membrane Environment

The Toll-like receptor 4 (TLR4)/myeloid differentiation factor 2 (MD-2) innate immunity system is a membrane receptor of paramount importance as therapeutic target. Its assembly, upon binding of Gram-negative bacteria lipopolysaccharide (LPS), and also dependent on the membrane composition, finally triggers the immune response cascade. We have combined ab-initio calculations, molecular docking, all-atom molecular dynamics simulations, and thermodynamics calculations to provide the most realistic and complete 3D models of the active full TLR4 complex embedded into a realistic membrane to date. Our studies give functional and structural insights into the transmembrane domain behavior in different membrane environments, the ectodomain bouncing movement, and the dimerization patterns of the intracellular Toll/Interleukin-1 receptor domain. Our work provides TLR4 models as reasonable 3D structures for the (TLR4/MD-2/LPS)₂ architecture accounting for the active (agonist) state of the TLR4, and pointing to a signal transduction mechanism across cell membrane. These observations unveil relevant molecular aspects involved in the TLR4 innate immune pathways and will promote the discovery of new TLR4 modulators.     

Conformational preferences of beta- and gamma-aminated proline analogues

Quantum mechanical calculations have been used to investigate how the incorporation of an amino group to the Cbeta- or Cgamma-positions of the pyrrolidine ring affects the intrinsic conformational properties of the proline. Specifically, a conformational study of the N-acetyl-N'-methylamide derivatives of four isomers of aminoproline, which differ not only in the beta- or gamma-position of the substituent but also in its cis or trans relative disposition, has been performed. To further understand the role of the intramolecular hydrogen bonds between the backbone carbonyl groups and the amino side group, a conformational study was also performed on the corresponding four analogues of (dimethylamino)proline. In addition, the effects of solvation on aminoproline and (dimethylamino)proline dipeptides have been evaluated using a self-consistent reaction field model, and considering four different solvents (carbon tetrachloride, chloroform, methanol and water). Results indicate that the incorporation of the amino substituent into the pyrrolidine ring affects the conformational properties, with backbone...side chain intramolecular hydrogen bonds detected when it is incorporated in a cis relative disposition. In general, the incorporation of the amino side group tends to stabilize those structures where the peptide bond involving the pyrrolidine nitrogen is arranged in cis. The aminoproline isomer with the substituent attached to the Cgamma-position with a cis relative disposition is the most stable in the gas phase and in chloroform, methanol and water solutions. Replacement of the amino side group by the dimethylamino substituent produces significant changes in the potential energy surfaces of the four investigated (dimethylamino)proline-containing dipeptides. Thus, these changes affect not only the number of minima, which increases considerably, but also the backbone and pseudorotational preferences. In spite of these effects, comparison of the conformational preferences, i.e., the more favored conformers, calculated for different isomers of aminoproline and (dimethylamino)proline dipeptides showed a high degree of consistency for the two families of compounds.     

Coacervative microextraction ultrasound-assisted back-extraction technique for determination of organophosphates pesticides in honey samples by gas chromatography–mass spectrometry

Coacervative microextraction ultrasound-assisted back-extraction technique (CME-UABE) is proposed for the first time for extracting and preconcentrating organophosphates pesticides (OPPs) from honey samples prior to gas chromatography–mass spectrometry (GC–MS) analysis. The extraction/preconcentration technique is supported on the micellar organized medium based on non-ionic surfactant. To enable coupling the proposed technique with GC, it was required to back extract the analytes into hexane. Several variables including, surfactant type and concentration, equilibration temperature and time, matrix modifiers, pH and buffers nature were studied and optimized over the relative response of the analytes. The best working conditions were as follows: an aliquot of 10 mL 50 g L⁻¹ honey blend solution was conditioned by adding 100 μL 0.1 mol L⁻¹ hydrochloric acid (pH 2) and finally extracted with 100 μL Triton X-114 100 g L⁻¹ at 85 °C for 5 min using CME technique. Under optimal experimental conditions, the enrichment factor (EF) was 167 and limits of detection (LODs), calculated as three times the signal-to-noise ratio (S/N = 3), ranged between 0.03 and 0.47 ng g⁻¹. The method precision was evaluated over five replicates at 1 ng g⁻¹ with RSDs ≤9.5%. The calibration graphs were linear within the concentration range of 0.3–1000 ng g⁻¹ for chlorpirifos; and 1–1000 ng g⁻¹ for fenitrothion, parathion and methidathion, respectively. The coefficients of correlation were ≥0.9992. Validation of the methodology was performed by standard addition method at two concentration levels (2 and 20 ng g⁻¹). The recoveries were ≥90%, indicating satisfactory robustness of the methodology, which could be successfully applied for determination of OPPs in honey samples of different Argentinean regions. Two of the analyzed samples showed levels of methidathion ranged between 1.2 and 2.3 ng g⁻¹.     

Depurated inversion method for orbital‐specific exchange potentials

This work presents exchange potentials for specific orbitals calculated by inverting Hartree–Fock wavefunctions. This was achieved by using a Depurated Inversion Method. The basic idea of the method relies on the substitution of Hartree–Fock orbitals and eigenvalues into the Kohn–Sham equation. Through inversion, the corresponding effective potentials were obtained. Further treatment of the inverted potential should be carried on. The depuration is a careful optimization which eliminates the poles and also ensures the fullfilment of the appropriate boundary conditions. The procedure developed here is not restricted to the ground state or to a nodeless orbital and is applicable to all kinds of atoms. As an example, exchange potentials for noble gases and term‐dependent orbitals of the lower configuration of Nitrogen are calculated. The method allows to reproduce the input energies and wavefunctions with a remarkable degree of accuracy.     

Thermodynamic properties at infinite dilution of several solutes in ethers by gas-liquid chromatography

Summary The thermodynamic properties of different solutes at infinite dilution have been determined at 323.15 K. Deviations from ideality are discussed in terms of different contributions. The activity coefficients are compared with the calculated values by the one group contribution method.     

A matrix-assisted laser desorption/ionization mass spectrometry approach to the lipid A from Mesorhizobium loti

The isolation, purification and analysis of the lipid A obtained from Mesorhizobium loti Ayac 1 BII strain is presented. Analysis of the carbohydrate moiety after acid hydrolysis by high-pH anion-exchange chromatography with pulse amperometric detection (HPAEC-PAD) showed the presence of glucosamine and galacturonic acid as the only sugar components. Gas chromatographic (GC) and GC/mass spectrometric (MS) analysis of the fatty acids revealed the presence of 3-OH-C12:0; 3-OH-C13:0; 3-OH-C20:0 and 27-OH-C28:0 among the major hydroxylated species. In addition, C16:0, C17:0, C18:0 and C 20:0 were shown as main saturated fatty acids. Different polyacylated species were evidenced by thin layer chromatography of lipid A, allowing the purification of two fractions. Ultraviolet matrix-assisted laser desorption/ionization time-of-flight (UV-MALDI-TOF) MS analysis with different matrices, in the positive- and negative-ion mode, was performed. The fast moving component revealed the presence of hexa-acylated species, varying in the fatty acid composition. Species containing three 3-OH fatty acids and a 27-OH-C28:0 fatty acid were observed. Individual ions within this family differ by +/-14 mass units. The slow moving component was enriched mainly in penta-acylated species. Among them, three subgroups were detected: the major one compatible with the sugar core bearing two 3-OH 20:0 fatty acids, a 3-OH 13:0 or a 3-OH 12:0 fatty acid, a 27-OH 28:0 fatty acid and one saturated fatty acid. Each signal differs in a C18:0 acyl unit from the corresponding hexa-acylated family. On the other hand, a subgroup bearing one 3-OH 20:0 fatty acid, one 27-OH 28:0 fatty acid and two non-polar fatty acids was shown. A minor subgroup compatible with structures containing two hydroxylated and three non-polar fatty acids was also detected. The results obtained showed that nor-harmane was an excellent matrix for charged lipid A structural studies in both, positive and negative ion modes.     

Analysis of pesticides and metabolites in Spanish surface waters by isotope dilution gas chromatography/mass spectrometry with previous automated solid-phase extraction Estimation of the uncertainty of the analytical results

A method based on isotope dilution gas chromatography/mass spectrometry (GC/MS) with automated solid-phase extraction (SPE) is described for the analysis of 32 pesticides and metabolites in surface waters. This approach consist in the use of nine isotopically labelled representative pesticides as internal standards, which allows high accuracy (trueness and precision) and sensitivity for most analysed compounds, as it is required for isotope dilution-based methods. Uncertainties associated with pesticide determination in real samples were estimated using quality assurance/quality control (QA/QC) data. For most pesticides expanded uncertainty was below 40%, according to the commonly established requirements for analytical results. Ninety three Spanish surface waters collected in June-July and September-November 2004 were analysed. Concentration and occurrence of pesticides were evaluated. These parameters were higher in the summer than in the autumn period. In summer four pesticides were found in more than 50% of the analysed samples and four compounds were detected above the concentration level of 1 microg/l (atrazine, terbutylazine, 3,4-dichloroaniline and fenitrothion), while in autumn percentage of detection was below 50% for all pesticides and only one compound (terbutylazine) exceeded 1 microg/l.