In situ studies of methanol decomposition and oxidation on Pd(111) by PM-IRAS and XPS spectroscopy

Methanol decomposition and oxidation on Pd(111) at millibar pressure were studied by in situ polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS), on-line gas chromatography and pre- and postreaction X-ray photoelectron spectroscopy (XPS). Various dehydrogenation products such as methoxy CH3O, formaldehyde CH2O, formyl CHO, and CO could be spectroscopically identified. Methanol oxidation proceeds via dehydrogenation to formaldehyde CH2O, which either desorbs or is further dehydrogenated to CO, which is subsequently oxidized to CO2. Carbonaceous overlayers that are present during the reaction may favorably affect the selectivity toward CH2O. The reaction takes place on metallic Pd, and no indications of an involvement of Pd surface oxide were observed.     

Chiral discrimination in lithium complexes of bis(5H-pyrroles) and bis(oxazolines)

The 1:1 and 2:1 complexes of chiral bis(5H-pyrroles) and bis(oxazolines) with the lithium cation have been studied by means of DFT methods (B3LYP/6-31G and B3LYP/6-311+G). The energetic, geometric, electronic, and orbital properties of the complexes have been analyzed. The chiral discrimination in the 2:1 complexes (homo vs heterochiral ones) indicate that in all the cases the heterochiral complexes are more stable than the homochiral ones, except for the tert-butyl derivatives. The chiral discrimination energies will be discussed on the basis of different parameters related to the lithium atom such as the N-Li distance, the orbital interaction between the lone pair of the nitrogen and an empty orbital of the lithium, and its atomic contribution to the total energy of the complexes.     

Solvent control on the selective, nonselective, and absent response of a partially substituted lower rim calix(4)arene derivative for soft metal cations (mercury(II) and silver(I)). Structural and thermodynamic studies

The solvent control on the ability of a partially substituted lower rim calix(4)arene derivative 5,11,17,23,tetra-tert-butyl[25,27-bis(hydroxy)-26,28-bis(ethylthioethoxy)]-calix(4)arene, 1 to host soft metal cations (Hg(II) and Ag(I)) is demonstrated through 1H NMR, electrochemical (conductance measurements), and thermodynamic characterization of the complexation process in a wide variety of solvents. Solvent-ligand interactions were assessed from 1H NMR measurements involving 1 and various solvents in CDCl3. Thus, the formation of a 1:1 1-CH3CN adduct is reported. As far as metal cations are concerned, depending on the medium their complexation with 1 was only observed for Hg(II) and Ag(I). Thus, in acetonitrile, 1 is more selective for Hg(II) relative to Ag(I) by a factor of 2.2 x 10(3). In methanol the selectivity is reversed to an extent that the affinity of 1 for Ag(I) is 1.4 x 10(3) higher than that for Hg(II). However, 1 is unable to recognize selectively these cations in N,N-dimethylformamide while in propylene carbonate the ability of 1 to interact with these cations is lost. An outstanding feature of thermodynamics emerges when an assessment is made of the ligand effect on the complexation of these cations and analogues calix(4)arene derivatives. Thus, in acetonitrile the thermodynamics of cation complexation by the hydrophilic cavity of a calix(4)arene containing mixed pendant groups is built up from thermodynamic data for the same process involving derivatives with common functionalities at the narrow rim. This is a unique example of the additive contribution of pendant arms in the field of thermodynamics of calixarene chemistry.     

CAROTENE and CYTOCHROME C DEPENDENT SURVIVAL KINETICS IN RESPONSE TO HIGH INTENSITY VISIBLE LIGHT IN THE SMUT FUNGUS Ustilago violacea

Abstract— Exposure of variously pigmented strains of Ustilago violacea to high intensity incandescent radiation resulted in the generation of three types of survival curves. High carotene, low cytochrome c containing strains of U. violacea were generally characterized by linear type I survival curves with slopes approximately equal to zero. Strains which lacked carotenes were characterized by exponential decay type II survival curves. A third survival curve, type III was observed with carotene accumulating strains which also contained large amounts of cytochrome c. The type III curves are characterized by an initial loss of viability, similar to the type II curves, followed by a recovery period, with eventual stability in survival. The survival curve type appears to be dependent on the relative mg quantities of cytochrome c and carotenes in the cells. Strains with carotene/cytochromec ratios of0–1 × 10^-1,3–15× 10^-1 and l6 × 10^-1 and above had type II, type III and type I survival curves, respectively.     

OXYGEN-DEPENDENT PHOTOSENSITIVITY and MITOTIC RECOMBINATION IN THE SMUT FUNGUS Ustilago violacea

Abstract— The effect of high intensity incandescent radiation on survival and mitotic recombination in the phlph + diploid strain of Ustilago violacea was studied with and without atmospheric O₂. In the presence of atmospheric O₂, strain phlph+ was characterized by photokilling to approximately 50% survival, and induction of mitotic recombination to about 60% by 90 min of light exposure. No photokilling and little induction of mitotic recombination were observed when light exposure was carried out in an 0₂ depleted environment. Photokilling and photo-induced mitotic recombination in U. violacea may be due to DNA damage or repair in response to a photosensitized reaction, involving an endogeneous photosensitizer.     

New Luminescent Lanthanide Tetrakis-Complexes NEt4[LnL4] Based on Dimethyl-N-Benzoylamidophosphate

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt₄[LnL₄] (Ln³⁺=La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt₄⁺ on the structure and properties of the tetrakis-complex [LnL4]^- is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of ⁵D₀→⁷F₄ transition, observed in the luminescence spectrum of NEt₄[EuL₄], is discussed based on theoretical calculations.     

Synthesis and Antifungal Activity of New Valine-Azole Hybrids

Russian Journal of General Chemistry - Herein, the synthesis of six new derivatives via molecular hybridization of imidazole or triazole and valine methyl ester as a rational design for accessing...     

Specific Recognition of β-Galactofuranose-Containing Glycans of Synthetic Neoglycoproteins by Sera of Chronic Chagas Disease Patients

Chagas disease (CD) can be accurately diagnosed by detecting Trypanosoma cruzi in patients’ blood using polymerase chain reaction (PCR). However, parasite-derived biomarkers are of great interest for the serological diagnosis and early evaluation of chemotherapeutic efficacy when PCR may fail, owing to a blood parasite load below the method’s limit of detection. Previously, we focused on the detection of specific anti-α-galactopyranosyl (α-Gal) antibodies in chronic CD (CCD) patients elicited by α-Gal glycotopes copiously expressed on insect-derived and mammal-dwelling infective parasite stages. Nevertheless, these stages also abundantly express cell surface glycosylphosphatidylinositol (GPI)-anchored glycoproteins and glycoinositolphospholipids (GIPLs) bearing nonreducing terminal β-galactofuranosyl (β-Galf) residues, which are equally foreign to humans and, therefore, highly immunogenic. Here we report that CCD patients’ sera react specifically with synthetic β-Galf-containing glycans. We took a reversed immunoglycomics approach that entailed: (a) Synthesis of T. cruzi GIPL-derived Galfβ1,3Manpα-(CH₂)₃SH (glycan G29_SH) and Galfβ1,3Manpα1,2-[Galfβ1,3]Manpα-(CH₂)₃SH (glycan G32_SH); and (b) preparation of neoglycoproteins NGP29b and NGP32b, and their evaluation in a chemiluminescent immunoassay. Receiver-operating characteristic analysis revealed that NGP32b can distinguish CCD sera from sera of healthy individuals with 85.3% sensitivity and 100% specificity. This suggests that Galfβ1,3Manpα1,2-[Galfβ1,3]Manpα is an immunodominant glycotope and that NGP32b could potentially be used as a novel CCD biomarker.     

Green Synthesis of Gold and Silver Nanoparticles Using Leaf Extract of Capsicum chinense Plant

So far, several studies have focused on the synthesis of metallic nanoparticles making use of extracts from the fruit of the plants from the genus Capsicum. However, as the fruit is the edible, and highly commercial, part of the plant, in this work we focused on the leaves, a part of the plant that is considered agro-industrial waste. The biological synthesis of gold (AuNPs) and silver (AgNPs) nanoparticles using aqueous extracts of root, stem and leaf of Capsicum chinense was evaluated, obtaining the best results with the leaf extract. Gold and silver nanoparticles synthesized using leaf extract (AuNPs-leaf and AgNPs-leaf, respectively) were characterized by UV-visible spectrophotometry (UV-Vis), Fourier Transform Infrared Spectroscopy with Attenuated Total Reflection (FTIR-ATR), X-ray Photoelectron Spectroscopy (XPS), Ultra Hight Resolution Scanning Electron Microscopy coupled to Energy-Dispersive X-ray spectroscopy (UHR-SEM-EDX) and Transmission Electron Microscopy (TEM), and tested for their antioxidant and antimicrobial activities. In addition, different metabolites involved in the synthesis of nanoparticles were analyzed. We found that by the use of extracts derived from the leaf, we could generate stable and easy to synthesize AuNPs and AgNPs. The AuNPs-leaf were synthesized using microwave radiation, while the AgNPs-leaf were synthesized using UV light radiation. The antioxidant activity of the extract, determined by ABTS, showed a decrease of 44.7% and 60.7% after the synthesis of the AuNPs-leaf and AgNPs-leaf, respectively. After the AgNPs-leaf synthesis, the concentration of polyphenols, reducing sugars and amino acids decreased by 15.4%, 38.7% and 46.8% in the leaf extract, respectively, while after the AuNPs-leaf synthesis only reducing sugars decreased by 67.7%. These results suggest that these groups of molecules are implicated in the reduction/stabilization of the nanoparticles. Although the contribution of these compounds in the synthesis of the AuNPs-leaf and the AgNPs-leaf was different. Finally, the AgNPs-leaf inhibited the growth of S. aureus, E. coli, S. marcescens and E. faecalis. All of them are bacterial strains of clinical importance due to their fast antibiotic resistance development.     

Iron/multiwalled carbon nanotube (Fe/MWCNT) hybrid materials characterization: thermogravimetric analysis as a powerful characterization technique

Journal of Thermal Analysis and Calorimetry - Nanomaterials and nanocomposites have gained relevance in science and technology due to their excellent properties. Therefore, the characterization of...