Synthesis, spectroscopic and thermal studies of the reactions of the donors piperazine and N,N′-dimethylpiperazine with σ- and π-acceptors

The interactions of the electron donors piperazine (PIP) and N,N′-dimethylpiperazine (DMPIP) with the σ-acceptor iodine and the π-acceptors tetracyanoethylene (TCNE) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) were studied spectrophotometrically in chloroform at 25 °C. The electronic and infrared spectra of the resulting charge-transfer complexes were recorded, in addition to thermal analysis. The results obtained showed that the stoichiometries of the reactions are not fixed and depend on the nature of both the donor and the acceptor. The formed CT-complexes have the formulas of , [(PIP)(TCNE)₂], [(PIP)(DDQ)₂], , [(DMPIP)(TCNE)₂] and [(DMPIP)(DDQ)₂]. A general mechanism explaining the formation of triiodide complexes was suggested.     

A self-similar behavior for the relative viscosity of concentrated suspensions of rigid spheroids

A viscosity model for suspensions of rigid particles with predictive capability over a wide range of particle volume fraction and shear conditions is of interest to quantify the transport of suspensions in fluid flow models. We study the shear viscosity of suspensions and focus on the effect of particle aspect ratio and shear conditions on the rheological behavior of suspensions of rigid bi-axially symmetric ellipsoids (spheroids). We propose a framework that forms the basis to microscopically parameterize the evolution of the suspension microstructures and its effect on the shear viscosity of suspensions. We find that two state variables, the intrinsic viscosity in concentrated limit and the self-crowding factor, control the state of dispersion of the suspension. A combination of these two variables is shown to be invariant with the imposed shear stress (or shear rate) and depends only on the particle aspect ratio. This self-similar behavior, tested against available experimental and numerical data, allows us to derive a predictive model for the relative viscosity of concentrated suspensions of spheroids subjected to low (near zero) strain rates. At higher imposed strain rates, one needs to constrain one of the state variables independently to constrain the state of dispersion of the suspension and its shear dynamic viscosity. Alternatively, the obtained self-similar behavior provides the means to estimate the state variables from the viscosity measurements made in the laboratory, and to relate them to microstructure rearrangements and evolution occurring during deformation.     

Antifungal Evaluation and Molecular Docking Studies of Olea europaea Leaf Extract,Thymus vulgaris and Boswellia carteri Essential Oil as Prospective Fungal Inhibitor Candidates

Background: The present study investigated the antifungal activity and mode of action of four Olea europaea leaf extracts, Thymus vulgaris essential oil (EO), and Boswellia carteri EO against Fusarium oxysporum. Methods: Fusarium oxysporum lactucae was detected with the internal transcribed spacer (ITS) region. The chemical compositions of chloroform and dichloromethane extracts of O. europaea leaves and T. vulgaris EO were analyzed using GC-MS analysis. In addition, a molecular docking analysis was used to identify the expected ligands of these extracts against eleven F. oxysporum proteins. Results: The nucleotide sequence of the F. oxysporum lactucae isolate was deposited in GenBank with Accession No. {"type":"entrez-nucleotide","attrs":{"text":"MT249304.1","term_id":"1824655600","term_text":"MT249304.1"}}MT249304.1. The T. vulgaris EO, chloroform, dichloromethane and ethanol efficiently inhibited the growth at concentrations of 75.5 and 37.75 mg/mL, whereas ethyl acetate, and B. carteri EO did not exhibit antifungal activity. The GC-MS analysis revealed that the major and most vital compounds of the T. vulgaris EO, chloroform, and dichloromethane were thymol, carvacrol, tetratriacontane, and palmitic acid. Moreover, molecular modeling revealed the activity of these compounds against F. oxysporum. Conclusions: Chloroform, dichloromethane and ethanol, olive leaf extract, and T. vulgaris EO showed a strong effect against F. oxysporum. Consequently, this represents an appropriate natural source of biological compounds for use in healthcare. In addition, homology modeling and docking analysis are the best analyses for clarifying the mechanisms of antifungal activity.     

IL-21 as a Predictor of Sustained Virologic Response in Patients with Chronic Hepatitis C Virus Infection

Fatty acid desaturases (FADs) catalyze the introduction of a double bond into acyl chains. Two FAD groups have been identified in plants: acyl-acyl carrier proteins (ACPs) and acyl-lipid or membrane-bound FAD. The former catalyze the conversion of 18:0 to 18:1 and to date have only been identified in plants. The latter are found in eukaryotes and bacteria and are responsible for multiple desaturations. In this study, we identified 82 desaturase gene and protein sequences from 10 grass species deposited in GenBank that were analyzed using bioinformatic approaches. Subcellular localization predictions of desaturase family revealed their localization in plasma membranes, chloroplasts, endoplasmic reticula, and mitochondria. The in silico mapping showed multiple chromosomal locations in most species. Furthermore, the presence of the characteristic histidine domains, the predicted motifs, and the finding of transmembrane regions strongly support the protein functionality. The identification of putative regulatory sites in the promotor and the expression profiles revealed the wide range of pathways in which fatty acid desaturases are involved. This study is an updated survey on desaturases of grasses that provides a comprehensive insight into diversity and evolution. This characterization is a necessary first step before considering these genes as candidates for new biotechnological approaches.     

Sémantique algébrique ďun système logique basé sur un ensemble ordonné fini

In order to modelize the reasoning of an intelligent agent represented by a poset T, H. Rasiowa introduced logic systems called “Approximation Logics”. In these systems a set of constants constitutes a fundamental tool. In this papers, we consider logic systems called L′_T without this kind of constants but limited to the case where T is a finite poset. We prove a weak deduction theorem. We introduce also an algebraic semantics using Hey ting algebra with operators. To prove the completeness theorem of the L′_T system with respect to the algebraic semantics, we use the method of H. Rasiowa and R. Sikorski for first order logic. In the propositional case, a corollary allows us to assert that it is decidable to know “if a propositional formula is valid”. We study also certain relations between the L′_T logic and the intuitionistic and classical logics.     

Novel Spectrophotometric Method for Determination of Macro-paracetamol via Reaction with Bromine

The reaction between Br2 and paracetamol(p-AAP) leads to the formation of a coloured product, which can be used for spectrophotometric determination of the p-AAP content in its pure form and in different pharmaceutical preparations with p-AAP. The stoichiometric composition of the reaction was found to be n(p-AAP)∶n(bromine)=1∶3. The effects of pH and time on the spectra of p-AAP-bromine redox reaction product were studied. The interference of different additives on the measured spectra of the obtained product was also studied. The results obtained by the present method were compared with those obtained by the standard method. The F- and t- test values were calculated for both of the applied procedures and they met a confidence level of 99%. The proposed procedure actually needs no separation of these drugs from their sources before analysis and was unaffected by interference of other phenolic compounds. The proposed method is simpler and faster than the repoeted ones.     

Copper(ii) ketimides in sp3 C–H amination

Commercially available benzophenone imine (HN CPh₂) reacts with β-diketiminato copper(ii) tert-butoxide complexes [Cu^II]–O^tBu to form isolable copper(ii) ketimides [Cu^II]–N CPh₂. Structural characterization of the three coordinate copper(ii) ketimide [Me₃NN]Cu–N CPh₂ reveals a short Cu-N_ketimide distance (1.700(2) Å) with a nearly linear Cu–N–C linkage (178.9(2)°). Copper(ii) ketimides [Cu^II]–N CPh₂ readily capture alkyl radicals R˙ (PhCH(˙)Me and Cy˙) to form the corresponding R–N CPh₂ products in a process that competes with N–N coupling of copper(ii) ketimides [Cu^II]–N CPh₂ to form the azine Ph₂C N–N CPh₂. Copper(ii) ketimides [Cu^II]–N CAr₂ serve as intermediates in catalytic sp³ C–H amination of substrates R–H with ketimines HN CAr₂ and ^tBuOO^tBu as oxidant to form N-alkyl ketimines R–N CAr₂. This protocol enables the use of unactivated sp³ C–H bonds to give R–N CAr₂ products easily converted to primary amines R–NH₂via simple acidic deprotection.

Commercially available benzophenone imine (HN CPh₂) reacts with β-diketiminato copper(ii) tert-butoxide complexes [Cu^II]–O^tBu to form isolable copper(ii) ketimides [Cu^II]–N CPh₂ that serve as intermediates in catalytic sp³ C−H amination via radical relay.     

Identification of a Sesquiterpene Lactone from Arctium lappa Leaves with Antioxidant Activity in Primary Human Muscle Cells

Many pathologies affecting muscles (muscular dystrophies, sarcopenia, cachexia, renal insufficiency, obesity, diabetes type 2, etc.) are now clearly linked to mechanisms involving oxidative stress. In this context, there is a growing interest in exploring plants to find new natural antioxidants to prevent the appearance and the development of these muscle disorders. In this study, we investigated the antioxidant properties of Arctium lappa leaves in a model of primary human muscle cells exposed to H₂O₂ oxidative stress. We identified using bioassay-guided purification, onopordopicrin, a sesquiterpene lactone as the main molecule responsible for the antioxidant activity of A. lappa leaf extract. According to our findings, onopordopicrin inhibited the H₂O₂-mediated loss of muscle cell viability, by limiting the production of free radicals and abolishing DNA cellular damages. Moreover, we showed that onopordopicrin promoted the expression of the nuclear factor-erythroid-2-related factor 2 (Nrf2) downstream target protein heme oxygenase-1 (HO-1) in muscle cells. By using siRNA, we demonstrated that the inhibition of the expression of Nrf2 reduced the protective effect of onopordopicrin, indicating that the activation of the Nrf2/HO-1 signaling pathway mediates the antioxidant effect of onopordopicrin in primary human muscle cells. Therefore, our results suggest that onopordopicrin may be a potential therapeutic molecule to fight against oxidative stress in pathological specific muscle disorders.