M13 bacteriophage is a key instrument in phage display applications, as well as a possible antibacterial therapeutic agent due to its highly restrictive bacterial pathogenesis, and other applications. The traditional phage purification process is usually achieved by gradient ultracentrifugation or a combination of precipitation, centrifugation and microfiltration. These approaches easily lead to long process times, high operational costs, phage aggregation and consequent product loss (approximately 60%). This work is thus focused on an alternative potential large-scale process to achieve high yield and purity while minimizing the operational costs. Electrostatic-based separation processes are also common biomolecules purification techniques. Although anion exchange chromatography has been used before to purify several viral particles, this technique has been poorly reported for the purification of M13 phage. In a recent work, our group has demonstrated the use of a predominant anion exchange process, where a polymeric ionic liquid (PIL) was used as an alternative separation matrix for M13 bacteriophage. In this work, a variety of system parameters was studied, including chemical structure of the cation and the anion, the crosslinker nature and its concentration, either in batch adsorption/elution or chromatographic operation mode. The PIL-based chromatographic operation mode revealed to be a suitable separation process for M13 from directly filtered E. coli supernatant, reaching over 70% M13 recovery and 4.6 purification factor in a single step. To our knowledge, this is the first time that PILs have been reported as separation agents for bioproducts from complex mixtures.

Agradecimentos: J.L.A. acknowledges funding from the Chemical Measurement and Imaging Program at the National Science Foundation (CHE-1413199). L.W.H thanks the São Paulo Research Foundation (FAPESP) for funding (grant 2012/22375-3)

The atmospheric concentration of CO2 is rising at an alarming pace, creating a pressing need for new and sustainable materials capable of capture and conversion. Poly(ionic liquid)s (PILs) are particularly effective catalysts for processes at or near atmospheric pressure. PILs industrial application poses challenges due to the low porosity of PIL, the limited batch conversion capacity, and the difficulties in reuse. To overcome these limitations, we herein propose the use of AEROPILs catalysts obtained from the integration of PILs in chitosan-based aerogels. These cost-effective highly porous materials have unique and tuneable porous properties making them not only ideal sustainable CO2 sorbents but also promising heterogeneous catalysts. While AEROPILs show moderate yields for CO2 conversion in batch mode, high catalytic activity was achieved when AEROPILs were used to catalyse the CO2 cycloaddition reaction to epoxides in packed-bed reactors operated under continuous flow. The catalytic activity and stability were maintained over 60 h without activity loss, and high productivity (space-time yield of 21.18 gprod h−1 L−1). This research reveals the pioneering use of AEROPILs to efficiently upcycle CO2 into cyclic carbonate under a continuous flow setup.

O desenvolvimento de soluções de armazenamento de energia seguras e eficientes é es- sencial para a transição de tecnologias à base de combustiveis fósseis para alternativas mais sustentáveis. Esta dissertação teve como objetivo conceber eletrólitos em gel (EGP) à base de celulose capazes de desempenho comparável com eletrólitos comerciais à base de carbonatos orgânico, aumentando a segurança. A formulação de novos eletrólitos baseou- se na racionalização do transporte de iões de lítio (Li+) e da dinâmica iônica subjacente. A hidroxipropilcelulose (HPC) foi usada para investigar as interações entre celulose e líquidos iônicos (LIs) derivados de imidazólio, utilizando ressonância magnética nuclear (RMN), rheo-RMN e reologia. Revelando o papel dos aniões e catiões na dissolução da celulose. Um solvente ternário para celulose, composto por um LI, [C4C1Im]Cl, e um solvente orgânico, dimetilsulfóxido (DMSO), foi explorado para estudar como a presença de água influencia a solubilidade do polímero e o emparelhamento iônico do LI. Este trabalho representa um passo em direcção um sistema mais complexo, aproximando-se da com- posição desejada para as formulações dos EGPs. Celulose foi modificada para produzir eletrólitos poliméricos (LIPs) denominados CellPILs, dos quais EGPs foram sintetizados, com o EGP derivado de metilimidazólio demonstrando o menor impedimento à difusão de Li+. EGPs foram produzidos a partir de celulose micro (MCC) e nanocristalina (NCC), com diferentes substituintes, para avaliar o impacto da cristalinidade do polímero e dos grupos introduzidos. A produção de EGPs também foi estudada com derivados não iônicos de celulose, como a metilcelulose (MC), produzindo géis termorreversíveis em DMSO e LIs ou LIPs. Após a dopagem com LiTFSI, a mobilidade de Li+ foi analisada, a presença que um LIP aniónico aumentou significativamente a mobilidade desses iões, aproximando- se do desempenho dos eletrólitos líquidos convencionais. EGPs baseados em MC foram avaliados para aplicação em supercapacitores e dispositivos eletrocrômicos, revelando resultados promissores. Técnicas de espectroscopia RMN foram utilizadas para investigar as interações entre celulose, LIs e misturas de LIs/solventes orgânicos, sendo depois também usadas para estudar o processo de gelificação e a dinâmica iônica dos EGPs.

Ionic liquids and poly(ionic liquid)s are interesting materials for CO2 capture, however, the deployment of their industrial application has been delayed on account of economic and technical issues that demand further optimization. The control over viscosity has serious consequences over the process, therefore, this work is focused on the study of imidazolium and pyrrolidinium-derived ILs and PILs with basic anions, such as acetate, hydroxide, and imidazolate that were synthesized and characterized by NMR, ATR-FTIR, TGA, and DSC. Different solvents and concentrations were tested in the preparation of PIL and IL solutions, which were used to capture CO2 by bubbling this gas at room temperature and atmospheric pressure (1 atm). The evaluation of the CO2 sorption capacity of each sample was carried out through the analysis of quantitative 13C NMR. The poly(1-vinyl-3-ethylimidazolium) acetate showed and sorption capacity of 5.68 mmol CO2/g PIL, and also the capacity to capture CO2 from exhaust gas mixture and the possibility to be recycled at least 5 times.

CO2 levels in the atmosphere are increasing exponentially. The current climate change effects motivate an urgent need for new and sustainable materials to capture CO2. Porous materials are particularly interesting for processes that take place near atmospheric pressure. However, materials design should not only consider the morphology, but also the chemical identity of the CO2 sorbent to enhance the affinity towards CO2. Poly(ionic liquid)s (PILs) can enhance CO2 sorption capacity, but tailoring the porosity is still a challenge. Aerogel’s properties grant production strategies that ensure a porosity control. In this work, we joined both worlds, PILs and aerogels, to produce a sustainable CO2 sorbent. PIL‐chitosan aerogels (AEROPILs) in the form of beads were successfully obtained with high porosity (94.6–97.0 %) and surface areas (270–744 m2/g). AEROPILs were applied for the first time as CO2 sorbents. The combination of PILs with chitosan aerogels generally increased the CO2 sorption capability of these materials, being the maximum CO2 capture capacity obtained (0.70 mmol g−1, at 25 °C and 1 bar) for the CHT:P[DADMA]Cl30% AEROPIL.

The imperative of addressing CO2 capture and utilization arises from the pressing concerns surrounding global climate change. Existing commercial technologies for CO2 capture, either require substantial energy consumption or suffer performance degradation in the presence of impurities. Consequently, mitigating greenhouse gas emissions poses persistent challenges that call for advancements in materials and technologies. This study focused on developing highly regenerable materials tailored for CO2 capture and subsequent conversion into higher-value products, such as cyclic carbonates. The effectiveness of CO2 capture and utilization in ionic liquids (ILs) and poly(ILs) (PILs) depends on multiple factors including ion pair nature, anion basicity, buffering capacity, and hydrogen bond-forming sites, with no single property emerging as the most crucial due to their synergistic interplay, which illustrates the complexity of these materials. Herein, novel porous materials based on PILs-chitosan aerogels (AEROPILs) were successfully obtained, boasting high porosity and surface areas. PILs were incorporated into the aerogel matrix through a simple and straightforward procedure, advancing the aerogel formulation methodology. Generally, the inclusion of PILs in chitosan aerogels augmented the CO2 sorption capability of these materials, with the highest CO2 capture capacity observed for the pyrrolidinium-based AEROPIL (C:P230%) with 0.70 mmol g−1, at 25 °C and 1 bar. After evaluating CO2 capture capacity, AEROPILs were optimized as metal-free heterogeneous catalysts for CO2 conversion. In batch reactions, catalysts such as pyrrolidinium-based cross-linked AEROPIL (C:E:M1:P280%) and ammonium-based cross-linked AEROPIL (C:G:P430%) exhibited superior CO2 conversion capacities and high selectivity. Transitioning AEROPILs to continuous flow systems was explored as a pivotal step toward process scalability. Optimal reaction conditions were identified as a temperature of 120 °C, a liquid flow rate of 0.05 mL min-1, and a CO2 flow rate of 0.15 mL min-1. The most efficient catalyst, C:E:M1:P280%, demonstrated a noteworthy productivity of 21.18 gprod h-1 L-1 and maintained stability over 60 hours. Notably, the catalyst preserved its morphology and porosity, underscoring the feasibility of industrial-scale implementation of this process.

The atmospheric concentration of CO2 is rising at an alarming pace, creating a pressing need for new and sustainable materials capable of capture and conversion. Poly(ionic liquid)s (PILs) are particularly effective catalysts for processes at or near atmospheric pressure. PILs industrial application poses challenges due to the low porosity of PIL, the limited batch conversion capacity, and the difficulties in reuse. To overcome these limitations, we herein propose the use of AEROPILs catalysts obtained from the integration of PILs in chitosan-based aerogels. These cost-effective highly porous materials have unique and tuneable porous properties making them not only ideal sustainable CO2 sorbents but also promising heterogeneous catalysts. While AEROPILs show moderate yields for CO2 conversion in batch mode, high catalytic activity was achieved when AEROPILs were used to catalyse the CO2 cycloaddition reaction to epoxides in packed-bed reactors operated under continuous flow. The catalytic activity and stability were maintained over 60 h without activity loss, and high productivity (space-time yield of 21.18 g (prod) /(h L). This research reveals the pioneering use of AEROPILs to efficiently upcycle CO2 into cyclic carbonate under a continuous flow setup.