PM3 semi-empirical study of stereoelectronic effects in the Baeyer-Villiger reaction

The Baeyer-Villiger reaction of polymethoxybenzaldehydes with peroxysuccinic acid (PSA) is studied theoretically. The semi-empirical SCF-MO/PM3 method has been used to study the reaction and to calculate the energy profiles. In addition, heat of formation computations and bond order analyses of the transition species along the reaction coordinates have been performed and are interpreted qualitatively in terms of electron flow through the system during aryl migration. Our results support the hypothesis that the second step is a concerted reaction. Our data support a definite effect of the substituent on the aryl migration. The theoretical predictions are in good agreement with experimental results.     

Two-Higgs-doublet type-II and -III models and $$t\rightarrow c h$$ at the LHC

We study the constraints of the generic two-Higgs-doublet model (2HDM) type-III and the impacts of the new Yukawa couplings. For comparisons, we revisit the analysis in the 2HDM type-II. To understand the influence of all involving free parameters and to realize their correlations, we employ a \(\chi \)-square fitting approach by including theoretical and experimental constraints, such as the S, T, and U oblique parameters, the production of standard model Higgs and its decay to \(\gamma \gamma \), \(WW^*/ZZ^*\), \(\tau ^+\tau ^-\), etc. The errors of the analysis are taken at 68, 95.5, and \(99.7~\%\) confidence levels. Due to the new Yukawa couplings being associated with \(\cos (\beta -\alpha )\) and \(\sin (\beta -\alpha )\), we find that the allowed regions for \(\sin \alpha \) and \(\tan \beta \) in the type-III model can be broader when the dictated parameter \(\chi _F\) is positive; however, for negative \(\chi _F\), the limits are stricter than those in the type-II model. By using the constrained parameters, we find that the deviation from the SM in \(h\rightarrow Z\gamma \) can be of \(\mathcal{O}(10~\%)\). Additionally, we also study the top-quark flavor-changing processes induced at the tree level in the type-III model and find that when all current experimental data are considered, we get \(Br(t\rightarrow c(h, H) )< 10^{-3}\) for \(m_h=125.36\) and \(m_H=150\) GeV, and \(Br(t\rightarrow cA)\) slightly exceeds \(10^{-3}\) for \(m_A =130\) GeV.     

Effect of carbon nanotubes dispersion on morphology, internal structure and thermal stability of electrospun poly(vinyl alcohol)/carbon nanotubes nanofibers

The current work reports the effect of multi walled carbon nanotubes and single walled carbon nanotubes dispersion on morphological, structural and thermal degradation of electrospun poly(vinyl alcohol) (PVA)/carbon nanotubes (CNTs) dispersed in sodium dodecyl sulfate (SDS) (PVA/CNTs–SDS) composites nanofibers. (PVA/CNTs–SDS) nanocomposites fibers were elaborated using the traditional electrospinning process to disperse and align CNTs into the fibers, especially for low CNTs loading fraction: 0.3 and 0.7 wt%. The morphology of the electrospun fibers was studied using the scanning electronic microscopy. The average diameter of the fibers changes significantly after the incorporation of the CNTs in the PVA. Furthermore, Fourier transform infrared spectroscopy elucidated the effect of CNTs on the crystallization of the PVA which was confirmed by X-ray diffraction analysis. Thermogravimetric analysis showed that the thermal stability of the composite fibers depends on the loading fraction and on the type of carbon nanotubes.     

Sea water desalination by dynamic layer melt crystallization: Parametric study of the freezing and sweating steps

This work aims at developing a dynamic layer crystallizer operated batchwise, for freezing desalination of sea water. The experiments were performed with water/NaCl solutions and with samples of sea water from Nice, Rabat and Marseille. The pilot crystallizer consists of a cooled tube immersed in a cylindrical double jacketed tank. The solution is poured into the tank and the crystallization takes place on the external surface of the tube, by applying a cooling ramp in the tube. The solution is agitated by air bubbling. The whole process involves the freezing step, leading to the crystallization of the ice layer and the sweating step, which consists of purifying in depth the ice layer by melting the impure zones. A parametric study on the effect of the operating parameters has allowed quantifying the role of the different key parameters of the freezing and sweating steps. Three experiments allowed reaching salinities lower than 0.5 g/kg, satisfying the standards of drinking water. The duration of the whole process dropped to only 8 h (5 h for freezing and 3 h for sweating), with a yield of sweating equal to about 50%, provided severe conditions were applied for sweating. Higher yields required longer times. Overall, the results show the feasibility of the technique.     

A sensor based on silver nanoparticles synthesized on carbon graphite sheets for the electrochemical detection of nitrofurazone: Application: Tap water,commercial milk and human urine

Nitrofurazone is a nitrofuran-family synthetic chemical that has been used to treat bacterial infections since 1993. Silver nanoparticles synthesized by the thermal technique on graphite carbon sheets under optimal conditions were used to develop a highly sensitive electrochemical sensor. The main experimental characteristics are optimized to assure that this sensor functions correctly. Scanning electron microscope, X-ray diffraction, infrared spectroscopy were used to determine the chemical composition and morphology of the prepared pastes. With a maximal reduction peak of La nitrofurazone observed at ?0.57V/Ag-NPs@CPE versus Ag/AgCl, this sensor demonstrated good electrocatalytic activity for the reduction of La nitrofurazone. The influence of phosphate buffer solution pH indicates that the numbers of protons and electrons in the reaction at the surface of our constructed sensor were the same. The LOD and LOQ were calculated to be 1.2 × 10^?8 M and 1.3 × 10^?7 M, respectively. Using the differential pulse voltammetry technique, the calibration curve was established in the concentration range of 10^?4 M to 2 × 10^?7 M. Our Ag-NPs@CPE sensors were evaluated in order to detect nitrofurazone in real contaminated samples tap water, commercial milk, and human urine, in particular. The electroanalysis results show a very high recovery rate of more than 96% on average, permitting us to determine that our sensors are functional under optimum working conditions.     

Impact of DNA Sequence and Oligonucleotide Length on a Polythiophene‐Based Fluorescent DNA Biosensor

DNA hybridization is a universal and specific mechanism for the recognition of biological targets. Some cationic polythiophene transducers sensitive to DNA structure have been previously utilized to detect such biomolecules. Further characterization of these systems indicates that both DNA sequence composition and length modulate the biosensor performance. It appears that different repeated sequence patterns cause different conformational changes of the polythiophene, from a more relaxed form to an extremely rigid one. A length difference between the DNA oligonucleotide probe and target has a detrimental effect on the fluorescent signal, but it can be attenuated by changing the sequence composition of the protruding target sequence. This demonstrates that the nature of DNA can be critical for hybridization‐based detection systems.

     

Covalent Functionalization of HiPco Single‐Walled Carbon Nanotubes: Differences in the Oxidizing Action of H2SO4 and HNO3 during a Soft Oxidation Process

The results of a study on the evolution of HiPco single‐walled carbon nanotubes during the oxidizing action of H₂SO₄ and HNO₃ are presented. The process conditions used have been chosen so as to avoid any significant damage to the nanotube structure. The type and level of functionalization, the location of the grafted functions on the surface of the nanotube and the changes in morphological characteristics of the samples were examined by using a wide and complementary range of analytical techniques. We propose an explanation for the differences in the oxidizing action of sulfuric and nitric acids. The combined results allow us to suggest possible reaction mechanisms that occur on the surface of the nanotube.     

Comparison of the Phytochemical Variation of Non-Volatile Metabolites within Mother Tinctures of Arnica montana Prepared from Fresh and Dried Whole Plant Using UHPLC-HRMS Fingerprinting and Chemometric Analysis

Arnica montana L. has been recognized for centuries as an herbal remedy to treat wounds and promote healing. It also has a long tradition of use in homeopathy. Depending on its medicinal utilization, standardization regulations allow different manufacturing processes, implying different raw materials, such as the whole arnica plant in its fresh or dried state. In this study, an untargeted metabolomics approach with UHPLC-HRMS/MS was used to cross-compare the phytochemical composition of mother tinctures of A. montana that were prepared from either fresh whole plant (fMT) matter or from oven-dried whole plant (dMT) matter. The multivariate data analysis showed significant differences between fMT and dMT. The dereplication of the HRMS and MS/MS spectra of the more discriminant compounds led to annotated quinic acid, dicaffeoyl quinic acids, ethyl caffeate, thymol derivatives and dehydrophytosphingosine, which were increased in fMT, while Amadori rearrangement products (ARP) and methoxyoxaloyl-dicaffeoyl quinic acid esters were enhanced in dMT. Neither sesquiterpene lactones nor flavonoids were affected by the drying process. This is the first time that a sphingosine, ethyl caffeate and ARP are described in A. montana. Moreover, putative new natural products were detected as 10-hydroxy-8,9-epoxy-thymolisobutyrate and an oxidized proline fructose conjugate, for which isolation and full structure elucidation will be necessary to verify this finding.     

Silicon‐Based Dielectric Metamaterials: Focus on the Current Synthetic Challenges

Metamaterials have optical properties that are unprecedented in nature. They have opened new horizons in light manipulation, with the ability to bend, focus, completely reflect, transmit, or absorb an incident wave front. Optically active metamaterials in particular could be used for applications ranging from 3D information storage to photovoltaic cells. Silicon (Si) particles are some of the most promising building blocks for optically active metamaterials, with high scattering efficiency coupled to low light absorption for visible frequencies. However, to date ideal Si building blocks cannot be produced by bulk synthesis techniques. The key is to find a synthetic route to produce Si building blocks between 75–200 nm in diameter of uniform size and shape, that are crystalline, have few impurities, and little to no porosity. This Review provides a theoretical background on Si optical properties for metamaterials, an overview of current synthetic methods and gives direction towards the most promising routes to ideal Si particles for metamaterials.     

Anti-Cancer Activity of Buthus occitanus Venom on Hepatocellular Carcinoma in 3D Cell Culture

Hepatocellular carcinoma (HCC) is the most dominant primary liver cancer, which can be caused by chronic hepatitis virus infections and other environmental factors. Resection, liver transplantation, and local ablation are only a few of the highly effective and curative procedures presently accessible. However, other complementary treatments can reduce cancer treatment side effects. In this present work, we evaluated the activity of Moroccan scorpion venom Buthus occitanus and its fractions obtained by chromatography gel filtration against HCC cells using a 3D cell culture model. The venom was fractionated by gel filtration chromatography, each fraction and the crude venom was tested on normal hepatocytes (Fa2N-4 cells). Additionally, the fractions and the crude venom were tested on MCTSs (multicellular tumor spheroids), and this latter was generated by cultivate Huh7.5 cancer cell line with WI38 cells, LX2 cells, and human endothelial cells (HUVEC). Our results indicate that Buthus occitanus venom toxin has no cytotoxic effects on normal hepatocytes. Moreover, it is reported that F3 fraction could significantly inhibit the MCTS cells. Other Protein Separation Techniques (High-performance liquid chromatography) are needed in order to identify the most active molecule.