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Ionic Liquids as Extreme Pressure Additives for Bearing Steel Applications
Publication . Donato, Mariana T.; Nautiyal, Pranjal; Deuermeier, Jonas; Branco, Luís C.; Saramago, Benilde; Colaço, Rogério; Carpick, Robert W.; DQ - Departamento de Química; Faculdade de Ciências e Tecnologia (FCT); LAQV@REQUIMTE; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); UNINOVA-Instituto de Desenvolvimento de Novas Tecnologias; DCM - Departamento de Ciência dos Materiais; Springer
The protection of steel surfaces from wear under extreme pressure conditions is of major importance in several industries as it provides better performance and longer life of machinery. The motivation for this work was to study the lubrication of steel by ionic liquids (ILs), which have recently emerged as greener alternatives to commercial lubricants and additives. Three ILs based on sulfur-containing anions, used as 2-wt% additives in polyethylene glycol base oil (MW 200; PEG 200), were tested in the lubrication of ASTM 52100 bearing steel contacts in extreme pressure conditions (under mixed lubrication with a Hertzian pressure of 1.12 GPa) using a mini traction machine (MTM). Due to the poor resistance to corrosion of bearing steel, a semi-ester of succinic acid derivative corrosion inhibitor (Lanxess RC 4801) was added to the mixtures at a 1 wt% concentration. The ILs 1-hexyl-methylimidazolium trifluoromethanesulfonate ([C6mim][TfO]) and 1-hexyl-4-picolinium trifluoromethanesulfonate ([C6-4-pic][TfO]) revealed promising results in terms of surface protection of bearing steel. In contrast, 4-picolinium hydrogen sulfate ([4-picH][HSO4]) as 2-wt% additive to PEG 200 + 1% RC 4801 did not show any improvement in wear performance compared to neat PEG 200 + 1% RC 4801. PEG 200 + 2% [C6mim][TfO] + 1%RC 4801 allowed for a decrease in wear up to ~ 76% and PEG 200 + 2% [C6-4-pic][TfO] + 1%RC 4801 up to ~ 46% when compared with neat PEG 200 + 1% RC 4801. Optical microscopy images suggest the formation of an adsorbed layer, which was further supported by chemical analysis via x-ray photoelectron spectroscopy (XPS) data for [C6mim][TfO]. Graphical abstract: (Figure presented.)
How reliable is the evaluation of DNA binding constants?
Publication . Dömötör, Orsolya; Binacchi, Francesca; Ribeiro, Nádia; Busto, Natalia; Gonzalez-García, Jorge; Garcia-España, Enrique; Correia, Isabel; Enyedy, Éva A.; Hamacek, Josef; Terenzi, Alessio; Basílio, Nuno; Barone, Giampaolo; Cavaco, Isabel; Biver, Tarita; LAQV@REQUIMTE; DQ - Departamento de Química; Elsevier Science Publisher B.V.
In all experimental sciences, the precision and reliability of quantitative measurements are paramount. This is particularly true when examining the interactions between small molecules and biomolecules/polyelectrolytes, such as DNAs/RNAs, and yet it is overlooked in most publications of thermodynamic binding parameters. This paper presents findings from COST Action 18202 “Network for Equilibria and Chemical Thermodynamics Advanced Research,” which assessed the consistency of data derived from the interactions of calf-thymus DNA (CT-DNA) with the fluorescent intercalator ethidium bromide (EB) through spectrofluorimetric titrations. We first discuss critical experimental aspects and propose a reference experimental protocol which can be used to calibrate procedures for the determination of nucleic acid binding equilibrium constants. We then fit the experimental points according to different procedures and analyse the results focusing on the statistical dispersion of the data, aiming at enlightening the strong and weak points of different fitting procedures. The implications of this work are significant, demonstrating how the statistical dispersion of experimental data can influence the interpretation of biochemical coordination mechanisms. Our study reveals that, despite rigorous protocol standardization, the determination of binding parameters remains sensitive to the choice of data fitting method, with deviations in the logarithmic stability constant (logK) values not falling below 5 % relative standard deviation (RSD), or ± 0.5 logK units for 95 % confidence. This variability evidences the critical need for standardized best practices in data treatment as well as experimental procedures. Although our study focuses on the EB/CT-DNA system through fluorescence titrations, the broader implications for other methodologies across various biochemical systems highlight the importance of this first-of-its-kind inter-laboratory comparison in advancing our understanding of biochemical coordination processes.
Liposomal nanoformulations of novel copper-based complexes exhibiting antimelanoma activity – In vitro and in vivo validation
Publication . Coelho, Mariana P.; Farinha, Pedro F.; Côrte-Real, Leonor; Ribeiro, Nádia; Luiz, Hugo; Pinho, Jacinta O.; Noiva, Rute; Godinho-Santos, Catarina; Reis, Catarina Pinto; Correia, Isabel; Gaspar, Maria Manuela; CENIMAT-i3N - Centro de Investigação de Materiais (Lab. Associado I3N); DCM - Departamento de Ciência dos Materiais; Elsevier
Melanoma stands as the most aggressive form of skin cancer. The lack of effective and safe therapies has led to the investigation of innovative strategies. The present work validates the in vitro and in vivo antimelanoma activity of new copper complexes of 8-hydroxyquinoline (8HQ) derivatives in free or liposomal forms. Firstly, the cytotoxic properties of several copper-based complexes were screened towards human (A375) and murine (B16F10) melanoma cell lines and human dermal fibroblasts or keratinocytes (HaCaT) cell lines. All the complexes presented lower IC50 values (<20 μM) than dacarbazine (DTIC) and temozolomide (TMZ), the positive controls (>80 μM). Aiming to solve low specificity against tumor cells and enhance its targetability to affected sites three metal-based complexes were selected, based on their antiproliferative properties, and incorporated in long blood circulating liposomes. One of them, di-2-(((2-morpholinoethyl)imino)methyl)quinolin-8-olCopper(II), designated as LCR35, was selected for further studies due to the highest incorporation parameters and cytotoxic properties observed. The antiproliferative activity of LCR35 was preserved after its association to liposomes. Moreover, in B16F10 cells this effect was potentiated. Furthermore, cell cycle analysis studies in A375 and B16F10 cell lines were performed to elucidate the mechanism of action of copper-based complex formulations. A cell cycle arrest at G2/M and G0/G1 phases in A375 and B16F10 cells, respectively, both in free and liposomal forms were observed. To validate the therapeutic potential of LCR35 two murine melanoma models were carried out: subcutaneous and metastatic. Pre-clinical studies demonstrated the high therapeutic effect of LCR35, especially after incorporation in liposomes, compared to control group or animals that received LCR35 Free and DTIC. Overall, in vitro and in vivo studies highlight the potential antimelanoma properties of the copper-based complex, LCR35.
Napyradiomycin-based coatings
Publication . Pereira, Isabel; Macedo, Helena; Ferreira, Inês; Gonçalves, Bárbara; Piçarra, Susana; Sobral, Rita G.; Diniz, Mário; Gaudêncio, Susana P.; DCT - Departamento de Ciências da Terra; UCIBIO - Applied Molecular Biosciences Unit; DCV - Departamento de Ciências da Vida; DQ - Departamento de Química; LAQV@REQUIMTE; Elsevier BV
This study introduces a groundbreaking approach to marine antifouling by incorporating napyradiomycins extracts, meroterpenoids derived from marine actinomycetes, into biocide-free coatings, establishing the first comprehensive assessment of their dual antimicro- and antimacrofouling potential. By leveraging naturally derived bioactives, this work pioneers a sustainable alternative to copper- and ivermectin-based formulations, aligning with circular bioeconomy and green chemistry principles. At low concentrations (31.25 µg/mL), napyradiomycin-based coatings demonstrated effective macrofouling prevention with no detectable toxicity, while higher concentrations (10 mg/mL) rivaled conventional coatings in efficacy and induced lethality. Uniquely, ecotoxicological evaluations using oxidative stress biomarkers, supported by mussels’ survival assays, revealed no significant adverse effects at the lower concentration, showcasing an environmentally friendly profile rarely achieved in antifouling solutions. Despite the promising results, limitations under current static laboratory conditions include no antibiofilm activity and the need for long-term field validation under dynamic marine environments. These challenges, however, offer valuable opportunities for future research in formulation refinement, release profile optimization, and biocide loading thresholds. By combining antimacrofouling efficacy with low ecological impact and scalability potential, these coatings represent a promising advance in marine coating technology, warranting clear path forward for enhancing sustainability in marine industry practices while protecting marine biodiversity.
Plasma-enabled growth of vertically oriented carbon nanostructures for AC line filtering capacitors
Publication . Bundaleska, N.; Felizardo, E.; Santhosh, N. M.; Upadhyay, K. K.; Bundaleski, N.; Teodoro, O. M. N. D.; Botelho do Rego, A. M.; Ferraria, A. M.; Zavašnik, J.; Cvelbar, U.; Abrashev, M.; Kissovski, J.; Mão de Ferro, A.; Gonçalves, B.; Alves, L. L.; Montemor, M. F.; Tatarova, E.; CeFITec – Centro de Física e Investigação Tecnológica; DF – Departamento de Física; North-Holland | Elsevier
Self-standing vertically oriented carbon nanostructures (VCNs) were synthesized using a large-scale microwave plasma under low-pressure conditions, employing methane as a carbon precursor. The influence of plasma operational and substrate conditions on nanostructure growth and morphology were systematically studied. Furthermore, post-synthesis N-doping of VCNs with nitrogen content of 2.4 at% N was achieved using an Ar-N2 microwave plasma. Plasma-enabled direct deposition of VCNs, both doped and un-doped, onto nickel foils has been accomplished. The assessment of the developed nanostructures as electrodes in high-frequency AC filtering capacitors, has demonstrated an overall capacitance of approximately 480 µF at 100 Hz, with a cut-off frequency of 4 kHz for a phase angle of −45°. The excellent electrochemical performance can be attributed to the appropriate structural and morphological properties peculiar for the directly deposited on nickel foil VCNs providing binder-free electrode fabrication, thus enhancing the electrode's conductivity and charge transfer kinetics. This plasma-enabled approach for electrode design on a large scale, coupled with excellent filtering performance, paves the way for many applications in high-frequency scenarios, offering an environmentally friendly alternative to conventional electrolytic capacitors.
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Fundação para a Ciência e a Tecnologia
Programa de financiamento
Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017/2018) - Financiamento Programático
Número da atribuição
UIDP/00100/2020