First stage of the development of an eco-friendly detergent formulation for efficient removal of carbonized soil

Detergent formulations for cleaning a carbonized soil-degreasers-typically comprise surfactants, organic solvents, phosphate-based cleaning agents, and alkaline agents, which results in high pH values (>11) that raise human and environmental risks. It is important to develop eco-friendly and safer degreasers, while maintaining their cleaning efficiency. In this work, simple degreaser formulations, with a pH below 11 and without phosphates, were developed by using a mixture of solvent, surfactant, and water to remove carbonized soil. The efficiency of the new degreaser formulations (with 5 wt% solvent, 5 wt% nonionic or ionic surfactant, and 90 wt% water) was evaluated by an abrasion test in the removal of carbonized soil from ceramic and stainless steel surfaces and compared with a commercial product. The results obtained show that the formulations comprising isopropylene glycol (IPG) with C11-C13 9EOs and diethylene glycol butyl ether (BDG) with octyltrimethylammonium octanoate ([N1118][C8O2]) present the best cleaning efficiency for both surfaces. The composition of these formulations was optimized for each surface using a mixture design. The resulting formulations, despite having a simpler composition, a pH lower than 11, and being phosphate-free, presented a cleaning efficiency equal or slightly higher than the commercial control. These results show that it is possible to design degreasers that are much less aggressive to the environment and user, while simultaneously fulfilling the market requirements.publishe

Mixtures of polymers and cholinium-based ionic liquids to tailor the phase diagrams and extraction efficiency of aqueous biphasic systems

Aqueous biphasic systems (ABS) are outstanding alternatives over conventional liquid-liquid extraction processes since it is avoided the use of volatile and hazardous organic solvents (VOCs). ABS are more biocompatible systems formed by two aqueous-rich phases that can be designed by combining different pairs of solutes (polymer-polymer, polymer-salt or salt-salt) above specific concentrations. In the past years, ABS have been studied as powerful techniques for purification, separation and extraction purposes. Ionic liquids (ILs) have been described as interesting fluids towards the development of more sustainable processes. Due to the ILs unique properties, their introduction in ABS led to systems with higher selectivity and extraction performance for a wide plethora of compounds. In fact, it was already shown that ILs allow to overcome the low hydrophilic-hydrophobic range of ABS composed of two polymers or one polymer and one inorganic salt. IL-based ABS formed with polyethylene glycol (PEG) polymers were recently introduced and a successful control of the phase polarities, through the manipulation of the IL chemical structure, was demonstrated. Lately, it was also demonstrated that a new class of natural-derived cholinium-based ILs are capable of undergoing two phase separation by the addition of PEGs with different molecular weights. In the present work, mixtures of PEGs with different molecular weights (400 and 2000 g/mol) were used to ascertain on the formation ability of ABS composed of water and cholinium-based ILs or salts. The results obtained indicate that the formation ability of these ABS increase with the content of PEG2000 over PEG400 (and follow a continuous increase), meaning that a close-fitting control on their phases polarity can be attained. These systems were then evaluated on their performance for extracting a series of alkaloids with different polarities, namely caffeine, theophylline, theobromine and nicotine. In general, the alkaloids partition extent to the most hydrophobic phase (PEG-rich) follows their polarity/hydrophobicity. In summary, it is here demonstrated that mixtures of polymers as phase-forming components of ABS allow to tailor the partition coefficients of different alkaloids and their use in the purification of added-value compounds from biomass extracts is straightforwardly foreseen.publishe

Improved recovery of ionic liquids from contaminated aqueous streams using aluminium-based salts{

The number of applications involving ionic liquids has dramatically increased in the past few years, and their production and use in a large scale will inevitably lead to their dispersion into water streams (either by wastewater disposal or accidental leakage). Studies on the removal and recovery of ionic liquids from wastewater streams are therefore of crucial importance, yet particularly scarce. In this work, the use of aluminium salts is proposed to concentrate and remove ionic liquids from aqueous solutions. Two aluminium-based salts (Al 2 (SO 4 ) 3 and AlK(SO 4 ) 2 ?12H 2 O) were used to treat various aqueous solutions of ionic liquids containing imidazolium-, pyridinium-and phosphonium-based fluids. The gathered results show the enhanced ability of these salts to remove and recover ionic liquids from aqueous media. The minimum recovery efficiency achieved was 96%, whereas for a large array of systems recoveries of circa 100% of ionic liquid were attained. The residual concentrations of ionic liquids in water range from 0.01 to 6 wt%. The results reported disclose a novel promising technique for the recovery and treatment of aqueous effluents contaminated with ionic liquids by using salts commonly employed in water treatment processes, allowing thus its easy scale-up and adaptation to new processes involving ionic liquids

Advances achieved by ionic-liquid-based materials as alternative supports and purification platforms for proteins and enzymes

Ionic liquids (ILs) have been applied in several fields in which enzymes and proteins play a noteworthy role, for instance in biorefinery, biotechnology, and pharmaceutical sciences, among others. Despite their use as solvents and co-solvents, their combination with materials for protein- and enzyme-based applications has raised significant attention in the past few years. Among them, significant advances were brought by supported ionic liquids (SILs), in which ILs are introduced to modify the surface and properties of materials, e.g., as ligands when covalently bond or when physiosorbed. SILs have been mainly investigated as alternative supports for enzymes in biocatalysis and as new supports in preparative liquid chromatography for the purification of high-value proteins and enzymes. In this manuscript, we provide an overview on the most relevant advances by using SILs as supports for enzymes and as purification platforms for a variety of proteins and enzymes. The interaction mechanisms occurring between proteins and SILs/ILs are highlighted, allowing the design of efficient processes involving SILs. The work developed is discussed in light of the respective development phase and innovation level of the applied technologies. Advantages and disadvantages are identified, as well as the missing links to pave their use in relevant applications.publishe

Effectiveness of a combined surf and psychological preventive intervention with children and adolescents in residential childcare: A randomized controlled trial

Children and adolescents living in residential childcare have a higher prevalence of mental health problems as a result of a history of adverse childhood experiences. Therefore, this population should be a priority target for mental health preventive interventions. The current study analyses the effectiveness of the Wave by Wave surf therapy program, that combines surfing with a psychological group intervention, through a randomized controlled trial. Seventy-three youth (7-17 years) living in residential care participated in the study. Main mental health outcomes (adjustment problems, depression, anxiety, and wellbeing) and secondary outcomes (self-efficacy, self-regulation, sleep quality, physical activity, pro-social behavior, and social connectivity) were assessed at pre- and post-intervention. The results indicated a significant impact of the intervention on mental health outcomes reported by the key residential worker, with medium to large effect sizes. Specifically, after the intervention, there was a significant reduction in the total emotional and behavioural problems, and a significant increase of youth pro-social behaviour and quality of life that was not observed for the waiting list group. There were no significant effects on other measures reported by the children (e.g., depression and anxiety, self-esteem, emotion regulation, social connectedness, sleep quality, physical activity) and on executive functions measures. The Wave by Wave program seems to be an effective intervention to reduce behavior problems and to promote pro-social behavior in a high-risk sample. The absence of significant effects on other dimensions may indicate the need of some complementary support to address specific difficulties of this population.Efectividad de una intervención preventiva psicológica y de surf combinada con niños y adolescentes en cuidado residencial: Un ensayo controlado aleatorizado. Los niños y adolescentes que viven en acogimiento residencial tienen una mayor prevalencia de problemas de salud mental. Por lo tanto, esta población debe ser un objetivo prioritario para las intervenciones preventivas de salud mental. El estudio actual analiza la efectividad del programa Wave by Wave, que combina el surf con una intervención psicológica grupal, a través de un ensayo controlado aleatorio. Setenta y tres jóvenes (7-17 años) que viven en acogimiento residencial participaron en el estudio. Los principales resultados de salud mental (problemas de ajuste, depresión, ansiedad y bienestar) y los resultados secundarios (autoeficacia, autorregulación, calidad del sueño, actividad física, comportamiento prosocial y conectividad social) se evaluaron antes y después de intervención. Los resultados indicaron un impacto significativo de la intervención sobre los resultados de salud mental reportados por el cuidador en la residencia. Específicamente, después de la intervención, hubo una reducción significativa en los problemas emocionales y conductuales totales, y un aumento significativo del comportamiento prosocial de los jóvenes y de la calidad de vida que no se observó en el grupo control. No hubo efectos significativos en otras medidas reportadas por los niños (ex., depresión y ansiedad, autoestima) y en las medidas de las funciones ejecutivas. El programa Wave by Wave parece ser una intervención efectiva para reducir los problemas de comportamiento y promover el comportamiento prosocial en una muestra de alto riesgo. La ausencia de efectos significativos en otras dimensiones puede indicar la necesidad de algún apoyo complementario para abordar las dificultades específicas de esta población.

Simultaneous Separation of Antioxidants and Carbohydrates From Food Wastes Using Aqueous Biphasic Systems Formed by Cholinium-Derived Ionic Liquids

project CICECO-Aveiro Institute of Materials, UID/CTM/50011/2019. Associate Laboratory for Green Chemistry-LAQV, FCT Ref. UID/QUI/50006/2019. POCI-01-0145-FEDER-016403. Investigator FCT project IF/00621/2015. Programa Mais Centro under project CENTRO-07-ST24-FEDER-002008. COMPETE: PEst-C/SAU/UI0709/2011.The food industry produces significant amounts of waste, many of them rich in valuable compounds that could be recovered and reused in the framework of circular economy. The development of sustainable and cost-effective technologies to recover these value added compounds will contribute to a significant decrease of the environmental footprint and economic burden of this industry sector. Accordingly, in this work, aqueous biphasic systems (ABS) composed of cholinium-derived bistriflimide ionic liquids (ILs) and carbohydrates were investigated as an alternative process to simultaneously separate and recover antioxidants and carbohydrates from food waste. Aiming at improving the biocompatible character of the studied ILs and proposed process, cholinium-derived bistriflimide ILs were chosen, which were properly designed by playing with the cation alkyl side chain and the number of functional groups attached to the cation to be able to create ABS with carbohydrates. These ILs were characterized by cytotoxicity assays toward human intestinal epithelial cells (Caco-2 cell line), demonstrating to have a significantly lower toxicity than other well-known and commonly used fluorinated ILs. The capability of these ILs to form ABS with a series of carbohydrates, namely monosaccharides, disaccharides and polyols, was then appraised by the determination of the respective ternary liquid-liquid phase diagrams at 25 degrees C. The studied ABS were finally used to separate carbohydrates and antioxidants from real food waste samples, using an expired vanilla pudding as an example. With the studied systems, the separation of the two products occurs in one-step, where carbohydrates are enriched in the carbohydrate-rich phase and antioxidants are mainly present in the IL-rich phase. Extraction efficiencies of carbohydrates ranging between 89 and 92% to the carbohydrate-rich phase, and antioxidant relative activities ranging between 65 and 75% in the IL-rich phase were obtained. Furthermore, antioxidants from the IL-rich phase were recovered by solid-phase extraction, and the IL was recycled for two more times with no losses on the ABS separation performance. Overall, the obtained results show that the investigated ABS are promising platforms to simultaneously separate carbohydrates and antioxidants from real food waste samples, and could be used in further related applications foreseeing industrial food waste valorization.publishersversionpublishe

Microfluidic-assisted electrospinning, an alternative to coaxial, as a controlled dual drug release system to treat inflammatory arthritic diseases

Inflammatory arthritic diseases are characterized by a persistent inflammation of the synovial tissues where tumor necrosis factor alpha (TNFα) and interleukin-6 (IL-6) pro-inflammatory cytokines are over-expressed, leading to progressive musculoskeletal disability. Methotrexate (MTX), a disease-modifying-anti-rheumatic drug (DMARD) commonly applied in their treatment, can be used in combination with biological-DMARDs as anti-TNFα antibody to improve the treatments efficacy. However, their systemic administration comes with severe side-effects and limited therapeutic efficacy due to their off-target distribution and short half-life. To overcome such limitations, encapsulation of clinically relevant concentrations of MTX and anti-TNFα antibody into polycaprolactone (PCL) or poly(vinyl-alcohol) (PVA) microfluidic-assisted or coaxial electrospun fibrous meshes is proposed as local controlled dual drug release systems. Release studies show that microfluidic-assisted electrospinning meshes encapsulating both drugs achieved higher concentrations than coaxials. Biological assays using human articular chondrocytes (hACs) and monocytic cells (THP-1 cell line) demonstrate that fibrous meshes encapsulating the drugs are non-toxic. The systems' efficacy is proved by a significant decrease of TNFα and IL-6 concentrations in conditioned medium of lipopolysaccharide (LPS)-stimulated THP-1 cells, especially in the presence of microfluidic-assisted electrospun meshes, when compared with THP-1 conditioned medium (59.5% and 83.9% less, respectively). Therefore, microfluidic-assisted electrospinning fibrous meshes with encapsulating drugs represent an alternative to coaxial, as a local therapy for inflammatory arthritis diseases.This work was supported by the Northern Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, for the Ph.D grant of Catarina Silva (UMINHO/BD/33/2016; NORTE-08-5369-FSE-000012), and by the Portuguese Science and Technology Foundation (FCT) for the cells project Cells4_ID (PTDC/BTM-SAL/28882/2017)

one-step extraction and separation of betalains and chlorophylls using thermoreversible aqueous biphasic systems

This work was partly developed within the scope of the projects CICECO-Aveiro Institute of Materials, LA/P/0006/2020 and the Associate Laboratory for Green Chemistry-LA/P/0008/2020, financed by national funds through the FCT/MCTES (PIDDAC). Publisher Copyright: © 2023 The Royal Society of Chemistry.Globally, up to 50% of root crops, fruits and vegetables produced is wasted. Beetroot stems and leaves fit into this scenario, with only a small fraction being used in cattle food. One way of approaching this problem is through their valorisation, by extracting and recovering valuable compounds present in this type of waste that could be used in other applications, while contributing towards a circular economy. In this work, a new integrated process using thermoreversible aqueous biphasic systems (ABS) composed of quaternary ammonium-based ionic liquids (ILs) and polypropyleneglycol 400 g mol−1 (PPG) is shown to allow the one-step extraction and separation of two pigment classes—betalains and chlorophylls—from red beet stems and leaves. The pigment extraction was carried out with a monophasic aqueous solution of the IL and PPG, whose phase separation was then achieved by a temperature switch, resulting in the simultaneous separation of chlorophylls and betalains into opposite phases. A central composite design was used to optimise the extraction parameters (time, temperature, and solid : liquid (S/L) ratio) of both pigment extraction yields, reaching at 20 °C, 70 min and a S/L ratio of 0.12 a maximum extraction yield of 6.67 wt% for betalains and 1.82 wt% for chlorophylls (per weight of biomass). Moreover, it is shown that aqueous solutions of ILs better stabilise betalains than the gold standard solvent used for the extraction method. Among the studied systems, the ABS comprising the IL N-ethyl-N-methyl-N,N-bis(2-hydroxyethyl) bromide ([N21(2OH)(2OH)]Br) presented the best separation performance, with an extraction efficiency of 92% and 95% for chlorophylls and betalains, respectively, for opposite phases. The pigments were removed from the respective phases using affinity resins, with high recoveries: 96% for betalains and 98% for chlorophylls, further allowing the IL reuse. Finally, the cyto- and ecotoxicities of the quaternary ammonium-based ILs were determined. The obtained results disclosed low to negligible toxicity in the thousands of mg L−1 range, with [N21(2OH)(2OH)]Br being harmless from an ecotoxicological point of view. Overall, it is shown here that the developed process is an innovative approach for the one-step extraction and selective separation of pigments contributing to the valorisation of waste biomass.publishersversionpublishe

Aqueous Biphasic Systems Composed of Ionic Liquids and Sodium Carbonate as Enhanced Routes for the Extraction of Tetracycline

Aqueous biphasic systems (ABS) using ionic liquids (ILs) offer an alternative approach for the extraction, recovery, and purification of biomolecules through their partitioning between two aqueous liquid phases. In this work, the ability of a wide range of ILs to form ABS with aqueous solutions of Na 2 CO 3 was evaluated. The ABS formed by IL 1 water 1 Na 2 CO 3 were determined at 25 C, and the respective solubility curves, tie-lines, and tie-line lengths are reported. The studied ILs share the common chloride anion, allowing the IL cation core, the cation isomerism, the presence of functionalized groups, and alkyl side chain length effects to be evaluated. An increase in the cation side alkyl chain length leads to a higher ability for liquid-liquid demixing whereas different positional isomers and the presence of an allyl group have no major influence in the phase diagrams behavior. Quaternary phosphoniumand ammonium-based fluids are more able to form an ABS when compared with imidazolium-, pyridinium-, pyrrolidinium-, and piperidium-based ILs. Moreover, the presence of an aromatic cation core has no major contribution to the formation of ABS when compared to the respective nonaromatic counterparts. Finally, to appraise on the systems applicability in downstream processing, selected systems were used for the partitioning of tetracyclines (neutral and salt forms) -a class of antibiotics produced by bacteria fermentation. Single-step extraction efficiencies for the IL-rich phase were always higher than 99% and confirm the great potential of ILs to be applied in the biotechnological field

Cold atmospheric plasma, a novel approach against bladder cancer, with higher sensitivity for the high-grade cell line

Antitumor therapies based on Cold Atmospheric Plasma (CAP) are an emerging medical field. In this work, we evaluated CAP effects on bladder cancer. Two bladder cancer cell lines were used, HT-1376 (stage III) and TCCSUP (stage IV). Cell proliferation assays were performed evaluating metabolic activity (MTT assay) and protein content (SRB assay). Cell viability, cell cycle, and mitochondrial membrane potential (Δψm) were assessed using flow cytometry. Reactive oxygen and nitrogen species (RONS) and reduced glutathione (GSH) were evaluated by fluorescence. The assays were carried out with different CAP exposure times. For both cell lines, we obtained a significant reduction in metabolic activity and protein content. There was a decrease in cell viability, as well as a cell cycle arrest in S phase. The Δψm was significantly reduced. There was an increase in superoxide and nitric oxide and a decrease in peroxide contents, while GSH content did not change. These results were dependent on the exposure time, with small differences for both cell lines, but overall, they were more pronounced in the TCCSUP cell line. CAP showed to have a promising antitumor effect on bladder cancer, with higher sensitivity for the high-grade cell line.info:eu-repo/semantics/publishedVersio