Copper mesoporous materials as highly efficient recyclable catalysts for the reduction of 4-nitrophenol in aqueous media

Two mesoporous-based catalysts with different nominal copper loads (10 and 24% w/w) were prepared from impregnation of the MCM-41 support with copper acetylacetonate: Cu/MCM-41-10 and Cu/MCM-41-24, respectively. Samples with a metallic charge similar to the nominal content were obtained and the mesoporous structure was retained after the impregnation. X-ray diffractograms evidenced the presence of CuO in the catalyst with the higher metal loading. The catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in aqueous medium, with an excess of NaBH4, was chosen as a model reaction to evaluate the catalytic activity of the Cu/MCM-41-10 and Cu/MCM-41-24 catalysts. The 4-NP concentrations at prefixed intervals were monitored using UV–Vis spectroscopy. The Cu-based catalysts led to almost 100% reduction of 4-NP to 4-AP, with the reaction time of 30 and 50 s, for Cu/MCM-41-10 and Cu/MCM-41-24 respectively. The reaction follows a pseudo-first order law, with a rate constant of 0.374 and 0.109 s−1 for Cu/MCM-41-10 and Cu/MCM-41-24, respectively. Both catalysts were stable and could be reused up to ten times in consecutive runs without any treatment between the cycles. The catalytic activity was retained without loss of efficiency, indicating the high stability of the MCM-41 based catalysts under the reaction conditions.Fil: Schlichter, Sofia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Rocha, Marian. Universidad de Porto; PortugalFil: Peixoto, Andreia F.. Universidad de Porto; PortugalFil: Pires, João. Universidade de Lisboa; PortugalFil: Freire, Cristina. Universidad de Porto; PortugalFil: Alvarez, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentin

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

Evaluation of the Extraction Temperature Influence on Polyphenolic Profiles of Vine-Canes (Vitis vinifera) Subcritical Water Extracts

This work focused on evaluating the possibility of using vineyard pruning wastes from two Portuguese Vitis vinifera varieties; Touriga Nacional (TN) and Tinta Roriz (TR), as new potential ingredients for the nutraceutical industry. An environmentally friendly extraction technique; namely subcritical-water extraction (SWE), was employed. The overall results indicate that phenolic acids were the major class of compounds quantified; being gallic acid the principal one. The highest value for total phenolic content (TPC) was obtained for the TR extract at 250 °C (181 ± 12 mg GAE/g dw). In terms of antioxidant activity; the DPPH values for the extracts obtained at 250 °C were approximately 4-fold higher than the ones obtained at 125 °C; with TR extract presenting the highest value (203 ± 22 mg TE/g dw). Thus, the TR extract obtained through SWE at 250 °C was selected to evaluate the scavenging activity and the in vitro effects on cells due to the best results achieved in the previous assays. This extract presented the ability to scavenge reactive oxygen species (O2●-, HOCl and ROO●). No adverse effects were observed in HFF-1 viability after exposure to extract concentrations below 100 μg/mL. This work demonstrated that vine-canes extracts could be a potential ingredient to nutraceutical industryO.D. is thankful for the research grant from project PTDC/BII-BIO/30884/2017—POCI-01-0145-FEDER-030884. D.P. is thankful for the PhD grant (SFRH/BD/144534/2019) financed by POPH-QREN and subsidized by the European Science Foundation and Ministério da Ciência, Tecnologia e Ensino Superior. M.M.M. (project CEECIND/02702/2017) and A.F.P. (DL57/2016–Norma transitória) are grateful for the financial support financed by national funds through FCT—Fundação para a Ciência e a Tecnologia, I.P. and to REQUIMTE/LAQV. The supply of the vineyard pruning is acknowledged to Sogrape, S.A. The authors are grateful to João Vasconcellos Porto for the provided identification of the studied plant material.info:eu-repo/semantics/publishedVersio

Bio-Guided Optimization of Cystoseira abies-marina Cosmeceuticals Extraction by Advanced Technologies

Cystoseira abies-marina (reclassified as Gongolaria abies-marina) is a brown seaweed species rich in meroterpenoids, presenting interesting antioxidant, antitumor, and anti-inflammatory activities. However, there is still a lot to uncover regarding the bioactive potential of this species, as evidenced by the lack of records of antiaging activities from Cystoseira abies-marina, making this macroalga an excellent candidate for studies of its cosmeceutical potential. Ultrasound-(UAE) and microwave-assisted extraction (MAE) are advanced sustainable technologies that are very efficient in enhancing bioactive compound extraction. Applying these extraction techniques to a new biological matrix often calls for optimizing the parameters toward the best extraction yield. Since Cystoseira abies-marina is a new matrix for both UAE and MAE techniques, the present work proposes the optimization of the extraction process, using a novel approach: instead of only focusing on increasing the yield, the goal of this work is to determine the parameters for UAE and MAE that lead to extracts with better antiaging activities. For this bio-guided approach, several Cystoseira abies-marina extracts were prepared by UAE and MAE under varying conditions of solvent, time, and algae/solvent ratios. Their antiaging activities were then determined, and all the results combined to unveil the conditions yielding extracts with higher cosmeceutical potential. Using statistical tools, it was found that, for UAE, the best conditions were ethyl acetate, 15 min, and a ratio of 1:4, which led to an extract with high yield, and causing the strong inhibition of tyrosinase and elastase. In turn, ethanol, 10 min, and a ratio of 1:4 were the best conditions for MAE, leading to the extract with the best antioxidant activity. The results show that the proposed bio-guided approach was effective in obtaining extracts with high cosmeceutical potential, unveiling the possibility of modulating an extract’s activity by changing the extraction method.FUNDING: Thanks are due to FCT—Fundação para a Ciência e a Tecnologia for supporting G.P.R.’s grant (SFRH/BD/144446/2019), through National and European Funds and co-financed by the European Social Fund through the Regional Operational Programme Centro 2020, as well as to FCT, the European Union, QREN, FEDER, and COMPETE, through funding the cE3c center (UIDB/00329/2020). This work received financial support from PT National Funds (FCT/MCTES, Fundação para a Ciência e a Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through projects UIDB/50006/2020 and UIDP/50006/2020. A.F.P. thanks FCT for funding through the Individual Call to Scientific Employment Stimulus (2020.01614.CEECIND/CP1596/CT0007).info:eu-repo/semantics/publishedVersio

Experimental Tests and Preliminary Life Cycle Assessment

Funding Information: Thanks are also due to FCT for the project PTDC/BII-BIO/30884/2017. A.F.P. and M.M.M. thank FCT for funding through the Individual Call to Scientific Employment Stimulus (ref. 2020.01614.CEECIND/CP1596/CT0007 and CEEC-IND/02702/2017, respectively). O.D. is thankful for the Ph.D. grant supported by FCT (2021.05322.BD). Funding Information: This work was funded by Portuguese funds through Fundação para a Ciência e a Tecnologia (FCT/MCTES) in the framework of the projects UIDB/50006/2020, UIDP/50006/2020, and EXPL/BII-BIO/0436/2021 and also by BIP Proof 2022/2023 through UI-Transfer, a cofunding project by European Union through COMPETE 2020-Portugal 2020, CIQUP, Centro de Investigação em Química da Universidade do Porto (UIDB/00081/2020), and IMS, Institute of Molecular Sciences (LA/P/0056/2020). Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.The control of the oxidative stability of biodiesel and blends of biodiesel with diesel is one of the major concerns of the biofuel industry. The oxidative degradation of biodiesel can be accelerated by several factors, and this is most critical in the so-called second generation biodiesel, which is produced from low-cost raw materials with lower environmental impacts. The addition of antioxidants is imperative to ensure the oxidative stability of biodiesel, and these are considered products of high commercial value. The antioxidants currently available on the market are from synthetic origin, so the existence/availability of alternative antioxidants of natural origin (less dependent on fossil sources) at a competitive price presents itself as a strong business opportunity. This work describes and characterizes a sustainable alternative to synthetic antioxidants used in the biodiesel market developed from extracts of vineyard pruning waste (VPW), which are naturally rich in phenolic compounds with antioxidant properties. A hydrothermal extraction process was applied as a more efficient and sustainable technology than the conventional one with the potential of the extracts as antioxidant additives in biodiesel evaluated in Rancitech equipment. The VPW extract showed comparable antioxidant activity as the commercial antioxidant butylated hydroxytoluene (BHT) typically used in biodiesel. The stability of the biodiesel is dependent from the amount of the extract added. Further, for the first time, the assessment of the environmental impacts of using natural extracts to control the oxidative stability of biodiesel in the production process is also discussed as a key factor of the process environmental sustainability.publishersversionpublishe

Cross-cultural adaptation and measurement properties of the Portuguese version of the Ankle Instability Instrument

Chronic ankle instability is one of the most common clinical conditions in the general population, especially in adult athletes. The cross-cultural adaptation of self-reported questionnaires that identify and classify this condition contribute to criteria standardization in research but also in rehabilitation. Aim of Study. To validate the Ankle Instability Instrument to the Portuguese population and to investigate its psychometric properties. Material and Methods. Linguistic and semantic equivalence of the original version of the Ankle Instability Instrument to the Portuguese population was firstly performed. The Portuguese version of the Ankle Instability Instrument was then applied to 81 higher education adult students, with (n = 59) and without history of ankle sprain (n = 22). Participants were evaluated two times with an interval of one week to assess the psychometric properties of the Portuguese version of the Ankle Instability Instrument. Results. In the reliability of binary responses based on the test retest, the tetrachoric correlation coefficient ranged from 0.99 to 1.00. In addition, the Kuder–Richardson coefficient was 0.79 suggesting good internal consistency. Conclusions. Test-retest showed an almost perfect match in all answers between the two moments, which seem to be related to sample characteristics. The internal consistency value was similar to the one obtained in the original version. The Portuguese version of the Ankle Instability Instrument is highly reliable and can be used in clinical practice.info:eu-repo/semantics/publishedVersio

Rhodium catalyzed hydroformylation of kaurane derivatives: A route to new diterpenes with potential bioactivity

Kaurenic and grandiflorenic acids are naturally occurring diterpenes whose biological activity has been described. Both acids contain an exocyclic methylenic double bond that allows further functionalization on their structure. In an attempt to expand the number of derivatives of these two natural products, we have undertaken a study on the hydroformylation of the methyl esters of the two acids and the trimethylsilyl ether of kaurenol. These substrates have been hydroformylated by using unmodified Rh catalysts, as well as Rh/PPh3 and Rh/tris-(o-t-butylphenyl)phosphite catalytic systems at 100 °C and 20 bar of CO/H2 (1:1). For the three substrates, the two Rh catalysts modified with P-donor ligands, produced high conversions and chemo- and regioselectivities in the diastereoisomeric pair of linear aldehydes. In all cases, the stereoselectivity observed is strongly dependent of the system used, being the most diastereoselective the least hindered unmodified Rh/CO catalyst. A correlation between the higher diastereoselectivity and the faster [beta]-elimination of the metal-alkyl intermediate observed in the unmodified system is discussed.http://www.sciencedirect.com/science/article/B6TF5-4RVMXFD-3/1/d27e671ad9e0b7fc325dfd0bdf413c7

The CHEK2 Variant C.349A>G Is Associated with Prostate Cancer Risk and Carriers Share a Common Ancestor.

The identification of recurrent founder variants in cancer predisposing genes may have important implications for implementing cost-effective targeted genetic screening strategies. In this study, we evaluated the prevalence and relative risk of the CHEK2 recurrent variant c.349A>G in a series of 462 Portuguese patients with early-onset and/or familial/hereditary prostate cancer (PrCa), as well as in the large multicentre PRACTICAL case-control study comprising 55,162 prostate cancer cases and 36,147 controls. Additionally, we investigated the potential shared ancestry of the carriers by performing identity-by-descent, haplotype and age estimation analyses using high-density SNP data from 70 variant carriers belonging to 11 different populations included in the PRACTICAL consortium. The CHEK2 missense variant c.349A>G was found significantly associated with an increased risk for PrCa (OR 1.9; 95% CI: 1.1-3.2). A shared haplotype flanking the variant in all carriers was identified, strongly suggesting a common founder of European origin. Additionally, using two independent statistical algorithms, implemented by DMLE+2.3 and ESTIAGE, we were able to estimate the age of the variant between 2300 and 3125 years. By extending the haplotype analysis to 14 additional carrier families, a shared core haplotype was revealed among all carriers matching the conserved region previously identified in the high-density SNP analysis. These findings are consistent with CHEK2 c.349A>G being a founder variant associated with increased PrCa risk, suggesting its potential usefulness for cost-effective targeted genetic screening in PrCa families

Global variation in diabetes diagnosis and prevalence based on fasting glucose and hemoglobin A1c

Fasting plasma glucose (FPG) and hemoglobin A1c (HbA1c) are both used to diagnose diabetes, but these measurements can identify different people as having diabetes. We used data from 117 population-based studies and quantified, in different world regions, the prevalence of diagnosed diabetes, and whether those who were previously undiagnosed and detected as having diabetes in survey screening, had elevated FPG, HbA1c or both. We developed prediction equations for estimating the probability that a person without previously diagnosed diabetes, and at a specific level of FPG, had elevated HbA1c, and vice versa. The age-standardized proportion of diabetes that was previously undiagnosed and detected in survey screening ranged from 30% in the high-income western region to 66% in south Asia. Among those with screen-detected diabetes with either test, the age-standardized proportion who had elevated levels of both FPG and HbA1c was 29-39% across regions; the remainder had discordant elevation of FPG or HbA1c. In most low- and middle-income regions, isolated elevated HbA1c was more common than isolated elevated FPG. In these regions, the use of FPG alone may delay diabetes diagnosis and underestimate diabetes prevalence. Our prediction equations help allocate finite resources for measuring HbA1c to reduce the global shortfall in diabetes diagnosis and surveillance

Repositioning of the global epicentre of non-optimal cholesterol

High blood cholesterol is typically considered a feature of wealthy western countries(1,2). However, dietary and behavioural determinants of blood cholesterol are changing rapidly throughout the world(3) and countries are using lipid-lowering medications at varying rates. These changes can have distinct effects on the levels of high-density lipoprotein (HDL) cholesterol and non-HDL cholesterol, which have different effects on human health(4,5). However, the trends of HDL and non-HDL cholesterol levels over time have not been previously reported in a global analysis. Here we pooled 1,127 population-based studies that measured blood lipids in 102.6 million individuals aged 18 years and older to estimate trends from 1980 to 2018 in mean total, non-HDL and HDL cholesterol levels for 200 countries. Globally, there was little change in total or non-HDL cholesterol from 1980 to 2018. This was a net effect of increases in low- and middle-income countries, especially in east and southeast Asia, and decreases in high-income western countries, especially those in northwestern Europe, and in central and eastern Europe. As a result, countries with the highest level of non-HDL cholesterol-which is a marker of cardiovascular riskchanged from those in western Europe such as Belgium, Finland, Greenland, Iceland, Norway, Sweden, Switzerland and Malta in 1980 to those in Asia and the Pacific, such as Tokelau, Malaysia, The Philippines and Thailand. In 2017, high non-HDL cholesterol was responsible for an estimated 3.9 million (95% credible interval 3.7 million-4.2 million) worldwide deaths, half of which occurred in east, southeast and south Asia. The global repositioning of lipid-related risk, with non-optimal cholesterol shifting from a distinct feature of high-income countries in northwestern Europe, north America and Australasia to one that affects countries in east and southeast Asia and Oceania should motivate the use of population-based policies and personal interventions to improve nutrition and enhance access to treatment throughout the world.Peer reviewe