Evaluation of calcipotriol transdermal permeation through pig,rat and mouse skin using liquid chromatography–tandem mass spectrometry

A rapid and sensitive liquid chromatography–tandem mass spectrometric method to evaluate the permeation and retention of calcipotriol in excised samples of pig, rat and mouse skin after application of a calcipotriol ointment has been developed and validated. After sample preparation of ointment, skin homogenate and receptor medium by liquid–liquid extraction, chromatography was performed on an Extend‐C₁₈ column using isocratic elution. Detection was by electrospray ionization in the negative ion mode using multiple‐reaction monitoring of the precursor to product ion transitions of calcipotriol at m/z 411.1 → 393.5, and of lovastatin (internal standard) at m/z 403.2 → 101.2. The assay was linear in all matrices with LLOQs of 1, 0.5 and 40 ng/mL for skin homogenate, receptor medium and ointment samples respectively. In terms of the permeation profiles, it was found that calcipotriol permeated through all skins to only a limited extent over 20 h after application but was efficiently retained in all skins at a level at 20 h of between 40% (pig) and 60% (rat and mouse) of the applied dose. This indicates that calcipotriol ointment has the potential to provide sustained therapeutic benefit in the treatment of psoriasis with minimal systemic side effects. Copyright © 2013 John Wiley & Sons, Ltd.     

Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing

The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384     

Environmental radioactivity of soils and sediments: Egyptian sector of the Nile valley

The activity concentrations of natural ⁴⁰K, ²³²Th, and ²³⁸U in 89 soil and 84 sediment samples collected over the entire Egyptian Nile River basin including the Nile delta are reported based on the results of epithermal neutron activation analysis. The average activity concentrations of ⁴⁰K, ²³²Th, and ²³⁸U equal to 15.3?±?6.6, 15.6?±?11.1 and 220?±?31 Bq/kg, respectively, are significantly lower than those reported for the Upper Continental Crust, World Average Sediments as well as World Average Soils, suggesting the presence of a considerable portion of mafic material, most probably originating from the Ethiopian High Plateau. Their average activity concentrations are statistically the same in soil and sediments, indicating that the Nile sediments and soil material are of the same origin. The main goal of this study was not only to estimate the radiological hazards but also to show the influence of sedimentary material transportable by the Blue Nile from the Ethiopian High Plateau. The different hazard indices like the radium equivalent, gamma index, external hazard as well as the internal hazard show a low radiological exposure either on direct contact or if local mud bricks are used in the construction of dwellings.     

An optical study of the D-D neutron irradiation-induced defects in Co-and Cu-doped ZnO wafers

Room-temperature photoluminescence and optical transmittance spectroscopy of Co-doped(1×1014,5×1016,and 1×1017cm-2) and Cu-doped(5×1016cm-2) ZnO wafers irradiated by D-D neutrons(fluence of 2.9×1010 cm-2) have been investigated.After irradiation,the Co or Cu metal and oxide clusters in doped ZnO wafers are dissolved,and the wu¨rtzite structure of ZnO substrate for each sample remains unchanged and keeps in high c-axis preferential orientation.The degree of irradiation-induced crystal disorder reflected from the absorption band tail parameter(E0) is far greater for doped ZnO than the undoped one.Under the same doping concentration,the Cu-doped ZnO wafer has much higher irradiation-induced disorder than the Co-doped one.Photoluminescence measurements indicate that the introduction rate of both the zinc vacancy and the zinc interstitial is much higher for the doped ZnO wafer with a high doping level than the undoped one.In addition,both crystal lattice distortion and defect complexes are suggested to be formed in doped ZnO wafers.Consequently,the Co-or Cu-doped ZnO wafer(especially with a high doping level) exhibits very low radiation hardness compared with the undoped one,and the Cu-doped ZnO wafer is much less radiation-hard than the Co-doped one.     

Electronic structure of platinum at ultrahigh pressure

Abstract

Platinum is studied, theoretically, under very high compression. The calculated equation of state is found to agree well with the recent experimental data. At V/V₀ = 0.4, where V₀ is the experimental equilibrium volume, we find a transition from the face centered cubic structure (fcc), found at ambient pressure, to the body centered cubic structure (bcc). The calculated transition pressure is 26 Mbar. The stabilization of the bcc structure is explained by the eigen value sum.     

Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]− Building Block Via Solid-State NMR Spectroscopy,Polarized Neutron Diffraction,and First-Principle Calculations

The local magnetic structure in the [Fe^III(Tp)(CN)₃]⁻ building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions.     

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr,iPr or iBu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu₃₀H₁₈{S₂P(OnPr)₂}₁₂] ( 1_H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1_H reveals an unprecedented central Cu₁₂ hollow icosahedron. Six faces of this icosahedron are capped by Cu₃ triangles, the whole Cu₃₀ core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S₆ symmetry. The locations of the 18 hydrides in 1_H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ₃-H, interstitial μ₄-H (seesaw) and μ₅-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the ¹H NMR spectrum of 1_H are in line with their coordination environment in the solid state, retaining the S₆ symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu₃₀H₁₈{Se₂P(OR)₂}₁₂] ( 2_H : R=iPr 3_H : R=iBu) were synthesized from their sulfur relative 1_H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1_H – 3_H . In addition, the reaction of 1_H with [Pd(PPh₃)₂Cl₂] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu₁₄H₂{S₂P(OnPr)₂}₆(C≡CR)₆] ( 4 : R=Ph; 5 : R = C₆H₄F).