Unveiling polymerization mechanism in pH-regulated supramolecular fibers in aqueous media

An amine functionalized C3-symmetric benzotrithiophene (BTT) monomer has been designed and synthetized in order to form pH responsive one-dimensional supramolecular polymers in aqueous media. While most of the reported studies looked at the effect of pH on the size of the aggregates, herein, a detailed mechanistic study is reported, carried out upon modifying the pH to trigger the formation of positively charged ammonium groups. A dramatic and reversible change in the polymerization mechanism and size of the supramolecular fibers is observed and ascribed to the combination of Coulombic repulsive forces and higher monomer solubility. Furthermore, the induced frustrated growth of the fibers is further employed to finely control the one-dimensional supramolecular polymerisation and copolymerization processes.Financial support from MINECO (CTQ2017-85393-P) and ERA-NET/European Commission/MINECO (EuroNanoMed2017-191/PCIN-2017-042) is acknowledged by T.T. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). M.G.I thanks Santander Talent Atraction Research (STAR2) for finantial support. This work was also financially supported by Spanish Ministry of Science and Innovation (PID2019-109450RB-I00/AEI/10.13039/501100011033), European Research Council/Horizon2020 (ERC-StG-757397), la Caixa Foundation (ID 100010434) and by the Generalitat de Catalunya (2017 SGR 01536) to S.P. and L.A

Elucidating dynamic behavior of synthetic supramolecular polymers in water by hydrogen/deuterium exchange mass spectrometry

A comprehensive understanding of the structure, self-assembly mechanism, and dynamics of one-dimensional supramolecular polymers in water is essential for their application as biomaterials. Although a plethora of techniques are available to study the first two properties, there is a paucity in possibilities to study dynamic exchange of monomers between supramolecular polymers in solution. We recently introduced hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize the dynamic nature of synthetic supramolecular polymers with only a minimal perturbation of the chemical structure. To further expand the application of this powerful technique some essential experimental aspects have been reaffirmed and the technique has been applied to a diverse library of assemblies. HDX-MS is widely applicable if there are exchangeable hydrogen atoms protected from direct contact with the solvent and if the monomer concentration is sufficiently high to ensure the presence of supramolecular polymers during dilution. In addition, we demonstrate that the kinetic behavior as probed by HDX-MS is influenced by the internal order within the supramolecular polymers and by the self-assembly mechanism.MINECO, Spain, Grant/Award Number: IJCI-2015-252389; Marie Curie FP7 SASSYPOL ITN program, Grant/Award Number: 607602; European Research Council, Grant/Award Number: 788618; Dutch Ministry of Education, Culture and Science, Grant/Award Number: 024.001.03

Applying reflective multicriteria decision analysis to understand the value of therapeutic alternatives in the management of gestational and peripartum anaemia in Spain

The objective of the FeminFER project was to assess the value of ferric carboxymaltose following a multicriteria decision analysis in obstetrics and gynaecology in Spain. Methods Ferric carboxymaltose (FCM) and ferrous sulphate were evaluated using the EVIDEM framework. Ten stakeholders participated to collect different perspectives. The framework was adapted considering evidence retrieved with a PICO-S search strategy and grey literature. Criteria/subcriteria were weighted by level of relevance and an evidence-based decision-making exercise was developed in each criterion; weights and scores were combined to obtain the value of intervention relative to each criterion/subcriterion, that were further combined into the Modulated Relative Benefit-Risk Balance (MRBRB). Results The most important criterion favouring FCM was Compared Efficacy/Effectiveness (0.183 +/- 0.07), followed by Patient Preferences (0.059 +/- 0.10). Only Direct medical costs criterion favoured FS (-0.003 +/- 0.03). MRBRB favoured FCM; 0.45 +/- 0.19; in a scale from -1 to + 1. Conclusions In conclusion, considering the several criteria involved in the decision-making process, participants agreed with the use of FCM according to its MRBRB

Polímeros supramoleculares funcionales: Diseño, síntesis, caracterización y aplicaciones

Tesis doctoral inédita leída en la Universidad Autónoma de Madrid. . Fecha de lectura: 1-1-2021