Luminescent ln-ionic liquids beyond europium

UID/QUI/50006/2019 POCI-01-0145-FEDER–007265 IST-ID/077/2018 DL 57/2016 UIDB/00100/2020Searching in the Web of Knowledge for “ionic liquids” AND “luminescence” AND “lan-thanide”, around 260 entries can be found, of which a considerable number refer solely or primarily to europium (90%, ~234). Europium has been deemed the best lanthanide for luminescent applications, mainly due to its efficiency in sensitization, longest decay times, and the ability to use its luminescence spectra to probe the coordination geometry around the metal. The remaining lanthanides can also be of crucial importance due to their different colors, sensitivity, and capability as probes. In this manuscript, we intend to shed some light on the existing published work on the remaining lanthanides. In some cases, they appear in papers with europium, but frequently in a subordinate position, and in fewer cases then the main protagonist of the study. All of them will be assessed and presented in a concise manner; they will be divided into two main categories: lanthanide compounds dissolved in ionic liquids, and lanthanide-based ionic liquids. Finally, some analysis of future trends is carried out highlighting some future promising fields, such as ionogels.publishersversionpublishe

Irradiation-responsive polysulfone film as a colorimetric UVA/UVB differentiator

Funding Information: This work was supported by the Associated Laboratory for Sustainable Chemistry-Clean Processes and Technologies-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). The NMR spectrometers are part of The National NMR Facility, supported by Fundação para a Ciência e a Tecnologia (RECI/BBB-BQB/0230/2012). This work was also supported by Fundação para a Ciência e a Tecnologia (FCT) through the projects UIDB/00100/2020, and by Fundação para a Ciência e a Tecnologia through the contract no IST-ID/077/2018 (Bernardo Monteiro). Cláudia C. L. Pereira thanks Fundação para a Ciência e a Tecnologia, MCTES, for the Norma transitória DL 57/2016 Program Contract. Fundação para a Ciência e a Tecnologia I.P. for the national funds in the scope of the project UIDB/00100/2020. Publisher Copyright: © 2023 The Royal Society of Chemistry.A wearable, small size, flexible and energy consumable free colorimetric detector of UVA radiation and UVB/UVA differentiation was created based on the peculiar stimuli-responsive behaviour of an imidazolium based ionic liquid. Semi-transparent polysulfone films are transformed into opaque and homogenous red films under UVA radiation (315-360 nm), while lower wavelength exposure (280-315 nm) induces increased emission detectable under dark light, with no colour modification of the film under visible light. Thermal analysis (TGA and DSC), spectroscopic analysis (FT-IR, 1H-NMR and UV-Vis), scanning electronic microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were conducted to elucidate confinement mechanism and irradiation effects.publishersversionpublishe

A Europium(III) Complex with an Unusual Anion–Cation Interaction: A Luminescent Molecular Thermometer for Ratiometric Temperature Sensing

This work was supported by the Associated Laboratory for Sustainable Chemistry‐Clean Processes and Technologies – 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) The NMR spectrometers are part of The National NMR Facility, supported by Fundação para a Ciência e a Tecnologia (RECI/BBB‐BQB/0230/2012). We also thank to RNEM – Portuguese Mass Spectrometry Network, ref. LISBOA‐01‐0145‐FEDER‐022125, supported by FCT and Lisboa Regional Operational Programme (Lisboa2020). This work has been supported by Fundação para a Ciência e a Tecnologia through the contract n° IST‐ID/077/2018 (Bernardo Monteiro), SFRH/BD/120985/2016 (Mani Outis). Cláudia C. L. Pereira thanks to Fundação para a Ciência e a Tecnologia, MCTES, for the Norma transitória DL 57/2016 Program Contract.An unusual thermally sensitive anion–cation interaction, which is characteristic of the anion [Eu(FOD)4]−, occurs in the complex [CHOL][Eu(FOD)4] (1; CHOL=choline; FOD=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) and affects both quantum yield and thermochromic behavior. This prompted the design of an Eu3+-based ratiometric thermometer that functions at temperatures up to 95 °C through a thermally excited state absorption of the Eu3+ ion. The reusable temperature-sensitive luminescent complex showed a range of relative sensitivity between 0.45 % C−1 at 25 °C, with an increase to 7.0 % C−1 at 95 °C. Confinement of compound 1 in a transparent film of polysulfone resulted in a higher thermal stability of 1 while its luminescence showed a strong temperature dependence.authorsversionpublishe

New Quantum-Dot-Based Fluorescent Immunosensor for Cancer Biomarker Detection

Cancer antigen 15-3 (CA 15-3) is a biomarker for breast cancer used to monitor response to treatments and disease recurrence. The present work demonstrates the preparation and application of a fluorescent biosensor for ultrasensitive detection of the cancer antigen CA 15-3 protein tumor marker using mercaptopropionic-acid-functionalized cadmium telluride (CdTe@MPA) quantum dots (QDs) conjugated with CA 15-3 antibodies. First, the QDs were synthesized by the hydrothermal route, resulting in spherical nanoparticles up to 3.50 nm in diameter. Subsequently, the QD conjugates were characterized by Fourier transform infrared spectroscopy (FTIR), UV absorption, and fluorescence. The interaction between the conjugates and the protein was studied by fluorescence spectroscopy in buffer and in 10-fold diluted commercial human serum. Calibration in spiked serum samples gave a detection limit of 0.027 U/mL, 1000-fold lower than the clinical limit for CA 15-3 (25 U/mL to 30 U/mL), indicating that this is an ultrasensitive technique. In addition, a rapid response was obtained within 10 min. The biosensor was selective in the presence of the interfering serum proteins BSA, CEA, and CA-125, with a maximum interference of 2% for BSA. The percent recovery was close to 100% with maximum relative standard deviation (RSD%) values of 1.56. Overall, the developed CA 15-3 biosensor provides a simple and sensitive method for ultrasensitive monitoring of breast cancer, as well as the ability to detect other molecules of interest in human serum matrices.This research was funded by Fundação para a Ciência e Tecnologia, I.P, grant number 2022.09032.PTDCinfo:eu-repo/semantics/publishedVersio

Multifunctionality of the [C2mim][Ln(fod)4] series (Ln = Nd-Tm except Pm):magnetic, luminescent and thermochemical studies

A series of nine tetrakis lanthanide β-diketonate complexes of the type [C2mim][Ln(fod)4] (C2mim = 1-ethyl-3-methylimidazolium, fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) were prepared, with yields above 80%, and their thermochemical, photophysical and magnetic susceptibilities were evaluated. Thermochemical studies presented a rare and reversible conversion between two solid phases (polymorphism), characteristic of the [Ln(fod)4]− anion. Photophysical and magnetic studies revealed that Dy and Er presented the multifunctionality of being simultaneously SMMs and visible (Dy) or near infra-red (Er) emitters. The Nd, Ho and Tm analogues present characteristic emission bands in the NIR region (800–1200 nm), while Sm, Eu, Tb and Dy present emissions in the visible range. Magnetic susceptibility of Tb, Dy, Ho, Er and Tm salts were measured in the temperature range of 2–300 K, showing paramagnetic behaviour, although with different regimes, with AC susceptibility measurements, at different frequencies in the range of 10–10 000 Hz, providing evidence of slow magnetic relaxation processes for Gd, Dy and Er analogues with SMM behavior.publishe

Oxidative stress involving changes in Nrf2 and ER stress in early stages of Alzheimer's disease

AbstractOxidative stress and endoplasmic reticulum (ER) stress have been associated with Alzheimer's disease (AD) progression. In this study we analyzed whether oxidative stress involving changes in Nrf2 and ER stress may constitute early events in AD pathogenesis by using human peripheral blood cells and an AD transgenic mouse model at different disease stages. Increased oxidative stress and increased phosphorylated Nrf2 (p(Ser40)Nrf2) were observed in human peripheral blood mononuclear cells (PBMCs) isolated from individuals with mild cognitive impairment (MCI). Moreover, we observed impaired ER Ca2+ homeostasis and increased ER stress markers in PBMCs from MCI individuals and mild AD patients. Evidence of early oxidative stress defense mechanisms in AD was substantiated by increased p(Ser40)Nrf2 in 3month-old 3xTg-AD male mice PBMCs, and also with increased nuclear Nrf2 levels in brain cortex. However, SOD1 protein levels were decreased in human MCI PBMCs and in 3xTg-AD mice brain cortex; the latter further correlated with reduced SOD1 mRNA levels. Increased ER stress was also detected in the brain cortex of young female and old male 3xTg-AD mice. We demonstrate oxidative stress and early Nrf2 activation in AD human and mouse models, which fails to regulate some of its targets, leading to repressed expression of antioxidant defenses (e.g., SOD-1), and extending to ER stress. Results suggest markers of prodromal AD linked to oxidative stress associated with Nrf2 activation and ER stress that may be followed in human peripheral blood mononuclear cells

Karyotype and genome size of Iberochondrostoma almacai (Teleostei, Cyprinidae) and comparison with the sister-species I.lusitanicum

This study aimed to define the karyotype of the recently described Iberian endemic Iberochondrostoma almacai, to revisit the previously documented chromosome polymorphisms of its sister species I.lusitanicum using C-, Ag-/CMA3 and RE-banding, and to compare the two species genome sizes. A 2n = 50 karyotype (with the exception of a triploid I.lusitanicum specimen) and a corresponding haploid chromosome formula of 7M:15SM:3A (FN = 94) were found. Multiple NORs were observed in both species (in two submetacentric chromosome pairs, one of them clearly homologous) and a higher intra and interpopulational variability was evidenced in I.lusitanicum. Flow cytometry measurements of nuclear DNA content showed some significant differences in genome size both between and within species: the genome of I. almacai was smaller than that of I.lusitanicum (mean values 2.61 and 2.93 pg, respectively), which presented a clear interpopulational variability (mean values ranging from 2.72 to 3.00 pg). These data allowed the distinction of both taxa and confirmed the existence of two well differentiated groups within I. lusitanicum: one that includes the populations from the right bank of the Tejo and Samarra drainages, and another that reunites the southern populations. The peculiar differences between the two species, presently listed as “Critically Endangered”, reinforced the importance of this study for future conservation plans

Characterization of levan produced by a Paenibacillus sp. isolated from Brazilian crude oil

A levan-type fructooligosaccharide was produced by a Paenibacillus strain isolated from Brazilian crude oil, the purity of which was 98.5% after precipitation with ethanol and dialysis. Characterization by FTIR, NMR spectroscopy, GC-FID and ESI-MS revealed that it is a mixture of linear (26) fructosyl polymers with average degree of polymerization (DP) of 18 and branching ratio of 20. Morphological structure and physicochemical properties were investigated to assess levan microstructure, degradation temperature and thermomechanical features. Thermal Gravimetric Analysis highlighted degradation temperature of 218°C, Differential Scanning Calorimetry (DSC) glass transition at 81.47°C, and Dynamic Mechanical Analysis three frequency-dependent transition peaks. These peaks, corresponding to a first thermomechanical transition event at 86.60°C related to the DSC endothermic event, a second at 170.9°C and a third at 185.2°C, were attributed to different glass transition temperatures of oligo and polyfructans with different DP. Levan showed high morphological versatility and technological potential for the food, nutraceutical, and pharmaceutical industries.São Paulo Research Foundation (FAPESP) within Grants 2020/13271-6 and 2018/25511-1. Additionally, the authors acknowledge the financial support by National Council for Scientific and Technological Development – CNPq and by Coordination for the Improvement of Higher Education Personnel (CAPES), Finance Code 001. In addition, this study was supported by the Portuguese Science Foundation (FCT) under the scope of the strategic funding of UID/BIO/04469/2020 unit and the Project FOSYNBIO (POCI-01-0145-FEDER-029549).info:eu-repo/semantics/publishedVersio

Antiproliferative Activity Of Flavonoids From Croton Sphaerogynus Baill. (euphorbiaceae).

Croton sphaerogynus is a shrub from the Atlantic Rain Forest in southeastern Brazil. A lyophilized crude EtOH extract from leaves of C. sphaerogynus, obtained by maceration at room temperature (seven days), was suspended in methanol and partitioned with hexane. The purified MeOH phase was fractionated over Sephadex LH-20 yielding five fractions (F1-F5) containing flavonoids, as characterized by HPLC-DAD and HPLC-MS analyses. The antiproliferative activity of the crude EtOH extract, MeOH and hexane phases, and fractions F1-F5 was evaluated on in vitro cell lines NCI-H460 (nonsmall cell lung), MCF-7 (breast cancer), and U251 (glioma). The MeOH phase showed activity (mean log GI50 0.54) higher than the hexane phase and EtOH extract (mean log GI50 1.13 and 1.19, resp.). F1 exhibited activity against NCI-H460 (nonsmall cell lung) (GI50 1.2 μg/mL), which could be accounted for the presence of flavonoids and/or diterpenes. F4 showed moderate activity (mean log GI50 1.05), while F5 showed weak activity (mean log GI50 1.36). It is suggested that the antiproliferative activity of the crude EtOH extract and MeOH phase is accounted for a synergistic combination of flavonoids and diterpenes.201521280

Comparação da eficiência relativa de dois apetrechos de coleta de peixes em praias no baixo rio Purus, Amazonas, Brasil

Apesar das praias serem consideradas um dos sete mais importantes habitats aquáticos da Amazônia, poucos trabalhos foram realizados quanto ao levantamento de sua ictiofauna, principalmente quando utilizados diferentes apetrechos de coleta. Este trabalho teve como objetivo comparar a eficiência relativa de dois apetrechos, rede de cerco e malhadeira, ambos utilizados de forma ativa (arrasto), em três praias localizadas no baixo rio Purus. A rede de cerco apresentou maior número de espécies e indivíduos capturados, no entanto, a malhadeira apresentou maiores valores de biomassa total, representada principalmente por Siluriformes. A baixa similaridade da fauna de peixes capturada (38%) foi devido à exclusividade de espécies coletadas com cada apetrecho, 41 com rede de cerco e 32 com malhadeira. O presente trabalho mostra a importância de se utilizar diferentes apetrechos de coleta como forma de diminuir a seletividade inerente de cada um desses aparelhos, melhorando a efetividade de amostragens em ambientes pouco estudados