A molecular view on biopolymer@Ionic liquid materials

Funding Information: This work was funded by National Funds through FCT – Portuguese Foundation for Science and Technology, reference UIDB/50025/2020–2023 and PTDC/QUI-QFI/31508/2017 , POR Lisboa and PTNMR (ROTEIRO/0031/2013; PINFRA/22161/2016), co-financed by ERDF through COMPETE 2020, Portugal, POCI and PORL and FCT through PIDDAC ( POCI-01-0145-FEDER-007688 ). MZ acknowledges funding from European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 101026335 . MCC gratefully acknowledges PTNMR&i3N for the former researcher contract and FCT for the current researcher contract (2021.03255.CEECIND). Publisher Copyright: © 2022 Elsevier LtdFinding a cheap and easily recycling material that can capture CO2 under atmospheric pressure (1 atm) is of paramount importance. In this context, combining ionic liquids (ILs) with abundant and natural materials, such as chitin-based biopolymers, appears as an interesting alternative. In this work, four acetate-based ILs were selected to explore the solubility of chitin, chitosan, and carboxymethyl-chitosan. Using carboxymethyl-chitosan and biopolymer monomer units as models, different Nuclear Magnetic Resonance (NMR) techniques, namely, 1H, 13C, nuclear Overhauser effect spectroscopy, and spin-lattice relaxation, were performed to evaluate the dissolution. Shrimp shells were used as a chitin source. Through a simple acid/base treatment, it was possible to remove minerals and proteins, and use it to prepare biopolymer@IL materials for CO2 capture tests. Efficient CO2 sorption capacity was observed upon bubbling CO2 with a maximum of 2.32 mmolCO2/gsorbent. Under N2 bubbling, the system demonstrated excellent recycling capacity using a room temperature procedure that outperformed aqueous amine solutions recycling. The absence of heating and vacuum recycling procedures, combined with the use of N2 or compressed air is much more appealing for industrial applications.publishersversionpublishe

Revisiting ionic liquid structure‐property relationship: A critical analysis

grant number 201863/2014-6 UIDB/04378/2020 UIDB/50025/2020-2023 POCI-01-0145-FEDER-007688 PTDC/QUI-QFI/31508/2017 FCT-(ROTEIRO/0031/2013-PINFRA/22161/2016 UIDB/04378/2020In the last few years, ionic liquids (ILs) have been the focus of extensive studies concerning the relationship between structure and properties and how this impacts their application. Despite a large number of studies, several topics remain controversial or not fully answered, such as: the existence of ion pairs, the concept of free volume and the effect of water and its implications in the modulation of ILs physicochemical properties. In this paper, we present a critical review of state‐of-the‐art literature regarding structure–property relationship of ILs, we re‐examine analytical theories on the structure–property correlations and present new perspectives based on the existing data. The interrelation between transport properties (viscosity, diffusion, conductivity) of IL structure and free volume are analysed and discussed at a molecular level. In addition, we demonstrate how the analysis of microscopic features (particularly using NMR‐derived data) can be used to explain and predict macroscopic properties, reaching new perspectives on the properties and application of ILs.publishersversionpublishe

Characterization of Fungal Melanins from Black Stains on Paper Artefacts

This work was supported by Portuguese funds from FCT/MCTES through the CleanART research project (PTDC/EPH-PAT/0224/2014); the Associate Laboratory for Green Chemistry— LAQV (UIDB/50006/2020 and UIDP/50006/2020); the i3N Associate Laboratory and PTNMR (POCI01-0145-FEDER-007688; UIDB/50025/2020-2023, ROTEIRO/0031/2013–PINFRA/22161/2016); the iMed.ULisboa (UIDB/04138/2020), the fellowship number SFRH/BD/133447/2017 (T.G.P.) and the researcher contracts CEECIND/01474/2018 (S.O.S.) and 2021.03255.CEECIND (M.C.C).Melanins play a fundamental role in the biology and ecology of several fungal species. Unfortunately, this group of amorphous macromolecules also severely (and most times irreversibly) stains cultural heritage objects. Despite efforts made throughout the years, knowledge of the chemical composition and structure of melanins is still insufficient, which hampers the task of safely cleaning these colourants from cultural heritage materials in a targeted way without causing further deterioration. This work aimed therefore to contribute towards enlightening the characteristics of fungal melanins from three fungi that are common paper colonizers: Aspergillus niger, Chaetomium globosum and Cladosporium cladosporioides. The extracted melanins were characterized by FTIR, Raman, UV-vis, Solid-State NMR and MALDI-TOF MS spectroscopies and the effect of inhibitors of DHN-melanin and DOPA-melanin pathways on colony pigmentation and growth was evaluated. Although all the extracted colourants show a predominantly aromatic structure with carbonyl and phenolic groups, some differences between the melanins can be highlighted. Melanins obtained from Ch. globosum and Cl. cladosporioides exhibited similar structures and composition and both presented DHN-melanin characteristics, while A. niger’s melanins revealed a more complex and ordered structure, with a higher prevalence of highly conjugated carbonyls than the others, besides the additional presence of a yellow/green component. These conclusions cannot be overlooked while selecting targeted cleaning methodologies for melanin stains on cultural heritage materials.publishersversionpublishe

Enzyme-inspired dry-powder polymeric catalyst for green and fast pharmaceutical manufacturing processes

Funding Information: The authors thank financial support from Fundação para a Ciência e a Tecnologia , Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES Portugal), through project PTDC/EQU-EQU/32473/2017 , a Principal Investigator contract IF/00915/2014 (T.C.), and a doctoral grant SFRH/BDE/51907/2012 , a partnership from FCT/MCTES and the pharmaceutical company HOVIONE (R.V.). L.B.M. would like to acknowledge for FCT/MCTES funding with reference CEECIND/03810/2017. The NMR spectrometers in LabNMR@Cenimat are part of the National NMR Facility, supported by FCT (ROTEIRO/0031/2013 - PINFRA/22161/2016 ), co-financed by FEDER through COMPETE 2020, POCI, and PORL and FCT through PIDDAC ( POCI-01-0145-FEDER-007688 ; UID/CTM/50025/2020-2023 ). The Associate Laboratory Research Unit for Green Chemistry - Clean Technologies and Processes - LAQV is financed by national funds from FCT/MCTES ( UIDB/QUI/50006/2020 ) and cofunded by the ERDF under the PT2020 Partnership Agreement ( POCI-01-0145-FEDER-007265 ). We also acknowledge Dr. Luz Fernandes, REQUIMTE analytical services, for GC analysis. Publisher Copyright: © 2022Catalysis in pharma manufacturing processes is typically homogeneous, expensive and with hard catalyst recovery/regeneration. Herein an enzyme-inspired dry-powder molecularly imprinted polymeric (MIP) system was designed for fast, selective oxidation of a cholesterol derivative and easy catalyst regeneration. The strategy involved the synthesis of a template-monomer (T:M) complex followed by the crosslinked polymerization in supercritical carbon dioxide (scCO2). A 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-MIP catalyst is obtained after the template cleavage from the matrix, and the oxidation of the N[sbnd]H groups turns available TEMPO moieties within the MIP. The oxidation of benzyl alcohol, 5α-cholestan-3β-ol and cholic acid was fast, in high yield and with selective oxidation capacity.publishersversionpublishe

Sulfonic Acid-Functionalized (Bio)Materials as Catalysts for Efficient Amide Bond Synthesis

Funding Information: The authors thank Fundação para a Ciência e Tecnologia (FC&T) for project PTDC/BII‐BIO/30884/2017 and EXPL/BII‐BIO/0436/2021 and also for the researcher contract 2021.03255.CEECIND (M.C.C) and 2020.01614.CEECIND/CP1596/CT0007 (A.F.P.). Authors also thank the support by the Associate Laboratory for Green Chemistry – LAQV, which is financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020) and i3 N (LA/P/0037/2020, UIDP/50025/2020 and UIDB/50025/2020 . The National NMR Facility is supported by FC&T (ROTEIRO/0031/2013 – PINFRA/22161/2016, co‐financed by FEDER through COMPETE 2020, POCI, and PORL and FC&T through PIDDAC) and CERMAX through project 022162. We thank Prof. Dr. Carlos A. M. Afonso from the Faculty of Pharmacy, ULisboa for the scientific discussions on the experiments carried out with furfuryl alcohol derivatives. Publisher Copyright: © 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH.Sulfonic acid carbon-(bio)based and natural clays-based catalysts were prepared and investigated for the first time as heterogeneous catalysts for amide bond synthesis by a Ritter reaction. The different SO3H-catalysts were screened using benzyl alcohol and acetonitrile as model substrates, and MWCNT-CSP revealed to be an efficient catalyst, affording the amide in 75 % yield. The practical utility of the catalysts was demonstrated by a diverse range of amides, obtained from alcohols and nitriles, in moderate to good yields. Biomass derived platform alcohols, such as 5-HMF and furfuryl alcohol, were also tested as potential building blocks for the synthesis of biopolymers. The SO3H-catalysts revealed to be a highly efficient and environmentally friendly alternative to the conventional acid catalysts commonly used in the Ritter reaction.publishersversionpublishe

Molecular Interactions in Ionic Liquids: The NMR Contribution towards Tailored Solvents

Ionic liquids have been on the spotlight of chemical research field in the last decades. Their physical properties (low vapor pressure, thermal stability, and conductivity) and the possibility of fine tuning make them a versatile class of compounds for a wide range of applications, such as catalysis, energy, and material sciences. Ionic liquids can establish multiple intermolecular interactions with solutes such as electrostatic, van der Waals, or hydrogen bonds. The prospect of designing ionic liquid structures toward specific applications has attracted the attention to these alternative solvents. However, their rational design demands a molecular detailed view, and Nuclear Magnetic Resonance is a unique and privileged technique for this purpose, as it provides atomic resolution and at the same time enables the study of dynamic information. In this chapter, we provide an overview about the application of Nuclear Magnetic Resonance spectroscopy techniques as a methodology for the rational design of ionic liquids as solvents for small organic compounds, CO2 capture, and polymers such as cellulose focusing mainly in the last 10 years

Synthesis and characterization of Locust Bean Gum derivatives and their application in the production of nanoparticles

The development of LBG-based nanoparticles intending an application in oral immunization is presented. Nanoparticle production occurred by mild polyelectrolyte complexation, requiring the chemical modification of LBG. Three LBG derivatives were synthesized, namely a positively charged ammonium derivative (LBGA) and negatively charged sulfate (LBGS) and carboxylate (LBGC) derivatives. These were characterized by Fourier-transform infrared spectroscopy, elemental analysis, nuclear magnetic resonance spectroscopy, gel permeation chromatography, and x-ray diffraction. As a pharmaceutical application was aimed, a toxicological analysis of the derivatives was performed by both MTT test and LDH release assay. Several nanoparticle formulations were produced using LBGA or chitosan (CS) as positively charged polymers, and LBGC or LBGS as negatively charged counterparts, producing nanoparticles with adequate properties regarding an application in oral immunization.info:eu-repo/semantics/publishedVersio

The AEROPILs Generation: Novel Poly(Ionic Liquid)-Based Aerogels for CO2 Capture

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 oC and 1 bar) for the CHT:P[DADMA]Cl30% AEROPIL.FCT—Portuguese Foundation for Science and Technolog

Evidence of Strong Guest–Host Interactions in Simvastatin Loaded in Mesoporous Silica MCM-41

Funding Information: This research was funded by the Associate Laboratory for Green Chemistry LAQV, which is financed by national funds from FCT/MEC (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER—007265). This research was funded by the Interreg 2 Seas program 2014–2020, and co-funded by the European Regional Development Fund (FEDER) under subsidy contract 2S01-059_IMODE and 2S07-033_ Site Drug. This research was funded by the Program PHC PESSOA 2018 project nbr 4340/40868R. This research was funded by National Funds through FCT—Portuguese Foundation for Science and Technology, reference UIDB/00100/2020, UIDP/00100/2020, LA/P/0056/2020, UIDB/50025/2020-2023, and PTNMR (ROTEIRO/0031/2013; PINFRA/22161/2016), co-financed by ERDF through COMPETE 2020, Portugal, POCI and PORL and FCT through PIDDAC (POCI-01-0145-FEDER-007688). M.C.C. acknowledges PTNMR&i3N for the researcher contract. T. Cordeiro acknowledges Fundação para a Ciência e a Tecnologia (FCT) for the scholarship SFRH/BD/114653/2016. I. Matos acknowledges FCT for the Investigator FCT contract IF/01242/2014/CP1224/CT0008. Publisher Copyright: © 2023 by the authors.A rational design of drug delivery systems requires in-depth knowledge not only of the drug itself, in terms of physical state and molecular mobility, but also of how it is distributed among a carrier and its interactions with the host matrix. In this context, this work reports the behavior of simvastatin (SIM) loaded in mesoporous silica MCM-41 matrix (average pore diameter ~3.5 nm) accessed by a set of experimental techniques, evidencing that it exists in an amorphous state (X-ray diffraction, ssNMR, ATR-FTIR, and DSC). The most significant fraction of SIM molecules corresponds to a high thermal resistant population, as shown by thermogravimetry, and which interacts strongly with the MCM silanol groups, as revealed by ATR-FTIR analysis. These findings are supported by Molecular Dynamics (MD) simulations predicting that SIM molecules anchor to the inner pore wall through multiple hydrogen bonds. This anchored molecular fraction lacks a calorimetric and dielectric signature corresponding to a dynamically rigid population. Furthermore, differential scanning calorimetry showed a weak glass transition that is shifted to lower temperatures compared to bulk amorphous SIM. This accelerated molecular population is coherent with an in-pore fraction of molecules distinct from bulklike SIM, as highlighted by MD simulations. MCM-41 loading proved to be a suitable strategy for a long-term stabilization (at least three years) of simvastatin in the amorphous form, whose unanchored population releases at a much higher rate compared to the crystalline drug dissolution. Oppositely, the surface-attached molecules are kept entrapped inside pores even after long-term release assays.publishersversionpublishe

Asymmetric synthesis of N-aryl aziridines

The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (−)-8-phenylmenthol, (−)-quinine and (−)-Oppolzer’s sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer’s auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantioselection and a mechanism is proposed for the aziridination reaction