Synthesis of Tailored Perfluoro Unsaturated Monomers for Potential Applications in Proton Exchange Membrane Preparation

The aim of the present work is the synthesis and characterization of new perfluorinated monomers bearing, similarly to Nafion®, acidic groups for proton transport for potential and future applications in proton exchange membrane (PEM) fuel cells. To this end, we focused our attention on the synthesis of various molecules with (i) sufficient volatility to be used in vacuum polymerization techniques (e.g., PECVD)), (ii) sulfonic, phosphonic, or carboxylic acid functionalities for proton transport capacity of the resulting membrane, (iii) both aliphatic and aromatic perfluorinated tags to diversify the membrane polarity with respect to Nafion®, and (iv) a double bond to facilitate the polymerization under vacuum giving a preferential way for the chain growth of the polymer. A retrosynthetic approach persuaded us to attempt three main synthetic strategies: (a) organometallic Heck-type cross-coupling, (b) nucleophilic displacement, and (c) Wittig–Horner reaction (carbanion approach). Preliminary results on the plasma deposition of a polymeric film are also presented. The variation of plasma conditions allowed us to point out that the film prepared in the mildest settings (20 W) shows the maximum monomer retention in its structure. In this condition, plasma polymerization likely occurs mainly by rupture of the bond in the monomer molecule

Desarrollo de implantes protesicos personalizados mediante impresión 3D de metales para el tratamiento quirúrgico de defectos maxilares

La osteonecrosis mandibular es una patología que suele presentarse como efecto secundario de la radioterapia con que se tratan los procesos oncológicos de cabeza y cuello, o después de tratamientos prolongados con bifosfonatos. Su única solución posible consiste en la resección quirúrgica del hueso dañado seguida de una reconstrucción anatómico-funcional con placas metálicas e implantes de diversos materiales. Debido a la dificultad técnica de la cirugía y la mala calidad que suele presentar el hueso del paciente, dicha reconstrucción rara vez es satisfactoria, ni desde el punto de vista funcional, ni desde el estético. El desarrollo de tecnologías de impresión 3D de metales ha abierto la posibilidad de fabricar prótesis personalizadas, hechas a partir de datos de TAC del paciente, para darles la forma exacta del segmento a sustituir. El proyecto que presentamos partió de dos premisas: i) las prótesis personalizadas, fabricadas por sinterizado metálico suponen una alternativa viable, y que mejora la situación actual; y ii) la adición de elementos de ingeniería tisular podría implementar estas prótesis personalizadas, promoviendo su osteointegración. Las dos hipótesis se pusieron a prueba mediante la creación de un modelo de resección maxilar en un animal de tamaño medio (conejo), y el diseño de prótesis personalizadas a dicho defecto, que se fabricaron en aleación Ti6Al4V mediante fabricación aditiva. En un desarrollo posterior, estas prótesis se combinaron con biomateriales, biomoléculas y células mesenquimales. Los resultados obtenidos prueban la utilidad de la impresión 3D de prótesis maxilares personalizadas, y la mejora de su osteointegración mediante adición de elementos de ingeniería tisular.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Synthesis and Matrix Properties of α-Cyano-5-phenyl-2,4-pentadienic Acid (CPPA) for Intact Proteins Analysis by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

The effectiveness of a synthesized matrix, α-cyano-5-phenyl-2,4-pentadienic acid (CPPA), for protein analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) in complex samples such as foodstuff and bacterial extracts, is demonstrated. Ultraviolet (UV) absorption along with laser desorption/ionization mass spectrometry (LDI-MS) experiments were systematically conducted in positive ion mode under standard Nd:YLF laser excitation with the aim of characterizing the matrix in terms of wavelength absorption and proton affinity. Besides, the results for standard proteins revealed that CPPA significantly enhanced the protein signals, reduced the spot-to-spot variability and increased the spot homogeneity. The CPPA matrix was successful employed to investigate intact microorganisms, milk and seed extracts for protein profiling. Compared to conventional matrices such as sinapinic acid (SA), α-cyano-4-hydroxycinnamic acid (CHCA) and 4-chloro-α-cyanocinnamic acid (CClCA), CPPA exhibited better signal-to-noise (S/N) ratios and a uniform response for most examined proteins occurring in milk, hazelnut and in intact bacterial cells of E. coli. These findings not only provide a reactive proton transfer MALDI matrix with excellent reproducibility and sensitivity, but also contribute to extending the battery of useful matrices for intact protein analysis

MALDI Mass Spectrometry: A Promising Non-Chromatographic Technique

In recent years, food safety and quality have become of great importance and have involved more public concern. Food quality is associated to food authentication and adulteration, or food features that include ingredients and/or additives as antioxidants and chemicals used to improve food taste, aroma and colour. Food safety is concerned with food contaminants and residues as pesticides, veterinary drugs, environmental contaminants, food processing and food packaging contaminants. As a result, demand for the development and the applications of more efficient methodologies to analyze food is significantly growing. In this perspective, a new discipline named foodomics has been recently introduced which applies advanced ‐omic sciences (genomics, proteomics, lipidomics, etc.) in food and nutrition fields for compound profiling, authenticity, food quality or safety, food bioactivity, toxicity issue and so on. Of course, for foodomics studies, mass spectrometry (MS) is considered an indispensable technique due to its intrinsic features, i.e. high sensitivity, selectivity and throughput. Among MS techniques, Matrix Assisted Laser Desorption Ionization (MALDI) has demonstrated a great potential in fast screening analyses for food quality and safety, since no chromatographic separation is usually needed. In this chapter, some MALDI MS quality control applications will be presented, based on proteomic and lipidomic approaches or devoted to the individuation of food contaminants

Selective Palladium(II)‐Catalyzed Dimerization of Styrenes and Acrylates in Molten Tetrabutylammonium Acetate as an Ionic Liquid

A method for the selective dimerization of styrenes and acrylates has been developed. The reaction is catalyzed by a very low amount of palladium acetate in molten tetrabutylammonium acetate without the need for any additional ligand. The use of this method enabled the coupling of substituted vinyl arenes in reasonable yields to give exclusively the (E,E)-1,4-diarylbutadiene motif within 7-10 h. Acrylates, on the other hand, exhibit higher reactivity, and the use of dibutyl acrylate resulted in the quantitative synthesis of dibutyl 2-methyleneglutarate in less than 2 h. This selectivity is unprecedented in the literature. The role of the ionic liquid and the different catalytic pathways involved in the two processes were also elucidated.The selective dimerization of styrenes and acrylates was possible with a very low amount of palladium acetate in molten tetrabutylammonium acetate. The coupling of substituted vinyl arenes gave exclusively the (E,E)-1,4-diarylbutadiene motif within 7-10 h, whereas butyl acrylate was converted into dibutyl 2-methyleneglutarate in less than 2 h. The catalytic pathways involved in the two processes were elucidated along with the role of the ionic liquid. imag