A versatile route for the fabrication of micro-patterned polylactic-acid (PLA)-based membranes with tailored morphology via breath figure imprinting.

Breath figure imprinting, based on surface instabilities combined with fast polymer evaporation in a humid environment, enables the creation of micro-patterned membranes with tailored pore sizes. Despite being a simple procedure, it is still challenging to fully understand the dynamics behind the formation of hierarchical structuring. In this work, we used the breath figure technique to prepare porous PLA-based (polylactic acid) membranes with two distinctive additives, polyvinylidene fluoride (PVDF) and zinc oxide nanoparticles (ZnO NPs). The selection of these additives was governed by their unique properties and the potential synergistic effects; when blended with PLA, the addition of NPs leads to more uniform structures with tunable characteristics and potential multifunctionality. This article sheds light on the multifaced interactions that intricate the interplays between PLA, PVDF, and ZnO, thus governing their assembly. Through a comprehensive investigation, we scrutinize the impact of blending PVDF and different concentrations of ZnO NPs on the morphology and chemical properties of the final self-assembled PLA membranes while presenting an advanced understanding of the potential applications of PLA-self-assembly porous membranes in various industrial sectors.

Cell and Tissue Imaging by TOF-SIMS and MALDI-TOF: An Overview for Biological and Pharmaceutical Analysis.

The potential of mass spectrometry imaging (MSI) has been demonstrated in cell and tissue research since 1970. MSI can reveal the spatial distribution of a wide range of atomic and molecular ions detected from biological sample surfaces, it is a powerful and valuable technique used to monitor and detect diverse chemical and biological compounds, such as drugs, lipids, proteins, and DNA. MSI techniques, notably matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) and time of flight secondary ion mass spectrometry (TOF-SIMS), witnessed a dramatic upsurge in studying and investigating biological samples especially, cells and tissue sections. This advancement is attributed to the submicron lateral resolution, the high sensitivity, the good precision, and the accurate chemical specificity, which make these techniques suitable for decoding and understanding complex mechanisms of certain diseases, as well as monitoring the spatial distribution of specific elements, and compounds. While the application of both techniques for the analysis of cells and tissues is thoroughly discussed, a briefing of MALDI-TOF and TOF-SIMS basis and the adequate sampling before analysis are briefly covered. The importance of MALDI-TOF and TOF-SIMS as diagnostic tools and robust analytical techniques in the medicinal, pharmaceutical, and toxicology fields is highlighted through representative published studies.

What is the fate of multi-lamellar liposomes of controlled size, charge and elasticity in artificial and animal skin?

Multi-lamellar liposomes (MLLs), prepared by shearing a lamellar phase composed of lipids (phosphatidylcholine) and surfactant (Tween 80®), were designed to control their size, charge and elasticity, the key parameters known to influence liposomes penetration through skin. Their size was tuned by the water content of the sheared lamellar phase, and by the surfactant-to-lipid ratio as was their elasticity. Their charge was varied by the incorporation of DPPG and DOTAP to confer a high negative or positive zeta potential, respectively. Couples of MLLs differing solely in one physicochemical parameter, the others kept constant, were compared to discriminate the influence of the key parameters on their penetration through a synthetic membrane, Strat-M™. Using confocal Raman microscopy, the kinetics of MLLs penetration was established for 40 h using a Franz cell dispositive under non-occlusive conditions. From these comparisons, we showed that their transversal diffusion cannot be predicted by one sole parameter but depends on a combination of their physicochemical characteristics that were enlightened. Two types of liposomes designed for topic and systemic diffusion and tested on dog-excised skin exhibited the predicted behavior. Eventually, a mechanism supported by complementary TEM analysis is proposed to shed light on MLLs skin penetration.

Topography Measurements Using High Mass Resolution Time-of-Flight Secondary Ion Mass Spectrometry: Application to Banknotes.

An unconventional approach using the time-of-flight secondary ion mass spectrometry (TOF-SIMS) technique to determine the height topography at the microscale is detailed in this work with an application to cotton paper banknotes. The study was conducted by determining the effect of all related factors and parameters on the height measurement by taking the simplest model made from two Post-it sheets. For each sample, the difference in the TOF of the same secondary ion coming from two different heights was successfully attributed to the step height of the studied areas' topography, which was measured using classic methods. The measurement was independent of the orientation of the topography with regard to the primary ion beam and the electron beam azimuth. Moreover, the adjustment of the extraction gap with different layers has no effect on such measurements. However, a range of the analyzer acceptance energy values could be considered to achieve the expected outcomes only if the different analyzers' component energies are also changing accordingly. Heights between 20 and 180 µm were successfully measured using this new method. An added benefit to this method over other height measurement methods is the ability to discern areas with different chemical compositions, which eventually may help aid understanding of the sample in question.

A Mineralogical Context for the Organic Matter in the Paris Meteorite Determined by A Multi-Technique Analysis.

This study is a multi-technique investigation of the Paris carbonaceous chondrite directly applied on two selected 500 × 500 µm² areas of a millimetric fragment, without any chemical extraction. By mapping the partial hydration of the amorphous silicate phase dominating the meteorite sample matrix, infrared spectroscopy gave an interesting glimpse into the way the fluid may have circulated into the sample and partially altered it. The TOF-SIMS in-situ analysis allowed the studying and mapping of the wide diversity of chemical moieties composing the meteorite organic content. The results of the combined techniques show that at the micron scale, the organic matter was always spatially associated with the fine-grained and partially-hydrated amorphous silicates and to the presence of iron in different chemical states. These systematic associations, illustrated in previous studies of other carbonaceous chondrites, were further supported by the identification by TOF-SIMS of cyanide and/or cyanate salts that could be direct remnants of precursor ices that accreted with dust during the parent body formation, and by the detection of different metal-containing large organic ions. Finally, the results obtained emphasized the importance of studying the specific interactions taking place between organic and mineral phases in the chondrite matrix, in order to investigate their role in the evolution story of primitive organic matter in meteorite parent bodies.

A click mediated route to a novel fluorescent pyridino-extended calix[4]pyrrole sensor: synthesis and binding studies.

A novel fluorescent aryl-extended phenoxycalix[4]pyrrole ditopic sensor with enhanced cation recognition properties was efficiently synthesized via click chemistry and characterized through both molecular fluorescence and nuclear magnetic resonance spectroscopy. Results demonstrate the selectivity of this fluorescent sensor for fluoride when taking into account its interaction with anions, while its cation binding properties showed selectivity for iron, and its sensing properties for several cations in dimethylsulfoxide. This work introduces a new ditopic receptor able to complex major environmentally relevant species and depicts the importance of click chemistry in the introduction of new tetra-chromophoric calix[4]pyrrole binding platforms with specific photophysical properties.

Kidney Lipidomics by Mass Spectrometry Imaging: A Focus on the Glomerulus.

Lipid disorders have been associated with glomerulopathies, a distinct type of renal pathologies, such as nephrotic syndrome. Global analyses targeting kidney lipids in this pathophysiologic context have been extensively performed, but most often regardless of the architectural and functional complexity of the kidney. The new developments in mass spectrometry imaging technologies have opened a promising field in localized lipidomic studies focused on this organ. In this article, we revisit the main works having employed the Matrix Assisted Laser Desorption Ionization Time of Flight (MALDI-TOF) technology, and the few reports on the use of TOF-Secondary Ion Mass Spectrometry (TOF-SIMS). We also present a first analysis of mouse kidney cortex sections by cluster TOF-SIMS. The latter represents a good option for high resolution lipid imaging when frozen unfixed histological samples are available. The advantages and drawbacks of this developing field are discussed.

High mass and spatial resolution mass spectrometry imaging of Nicolas Poussin painting cross section by cluster TOF-SIMS.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging using cluster primary ion beams is used for the identification of the pigments in the painting of Rebecca and Eliezer at the Well by Nicolas Poussin. The combination of the high mass resolution of the technique with a sub-micrometer spatial resolution offered by a delayed extraction of the secondary ions, together with the possibility to simultaneously identifying both minerals and organics, has proved to be the method of choice for the study of the stratigraphy of a paint cross section. The chemical compositions of small grains are shown with the help of a thorough processing of the data, with images of specific ions, mass spectra extracted from small regions of interest, and profiles drawn along the different painting layers. Copyright © 2016 John Wiley & Sons, Ltd.

PIXE as a complement to ICP-OES trace metal analysis in Sudanese medicinal plants.

This paper compares trace element concentrations (Ca, K, Sr, Fe, Mn, Zn, Ni, Cu, Co and Cr) in 27 Sudanese medical plants determined in parallel by PIXE and ICP-OES to get information on which technique is preferable at different matrices and element concentrations. PIXE correlates well to ICP-OES for Sr, Mn, Ca, K, Zn and Fe determinations. ICP-OES seems to be the superior technique over PIXE when measuring low concentrated elements (chromium, cobalt, nickel and copper) in the medicinal plants.