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1.
J Org Chem ; 2024 Sep 20.
Artículo en Inglés | MEDLINE | ID: mdl-39301849

RESUMEN

In this work, we explore the series of diradical(oid)s based on 2,2'-(5,11-dihydroindolo[3,2-b]carbazole-3,9-diyl)dimalononitrile (further referred to as PH). Hydrogen atoms in the central benzenoid (CB) ring of PH are substituted by the series of substituents with various lengths of π-conjugated chain and electron-donating or electron-withdrawing properties to study how they modulate the diradical character of the parent compound. The diradical character of molecules increases up to 88-89% by two groups doubly bonded to both sides of the CB ring of PH in para relative positions. This breaks the direct π-conjugation between unpaired electrons that gives rise to two radical centers and restricts the minimal polyradical identity of the compound to diradical. We show that diradicals and tetraradicals can be designed, and their polyradical character can be modulated by controlling the topology of π-conjugation as long as there is sufficient aromatic stabilization. Henceforth, the bridge between diradicals and tetraradicals is established, leading to the tetraradical(oid) molecule, which has been predicted to have narrow low-spin to high-spin energy gaps in our recent Letter.

2.
Phys Chem Chem Phys ; 26(31): 21303, 2024 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-39051927

RESUMEN

Correction for 'The nature of the electronic ground state of M2C (M = Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W) MXenes' by Néstor García-Romeral et al., Phys. Chem. Chem. Phys., 2023, 25, 31153-31164, https://doi.org/10.1039/D3CP04402E.

3.
Chem Biodivers ; : e202400652, 2024 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-38924342

RESUMEN

Commonly isolated from plants of Celastraceae family, pentacyclic triterpenoids have a broad spectrum of biological activities, such as antitumor, anti-inflammatory, antinociceptive properties, among others. Structural modifications in these triterpenoids can enhance their biological activity, as well as their selectivity, while improving their physicochemical and pharmacokinetic aspects. In this study, eight novel esters were synthesized: four derivatives of 3α-friedelinol (friedelan-3α-yl p-bromobenzoate (1a); friedelan-3α-yl naproxenate (1b); friedelan-3α-yl pent-4-ynoate (1c); friedelan-3α-yl undec-10-ynoate (1d)) and four derivatives of 3ß-friedelinol (friedelan-3ß-yl p-bromobenzoate (2a); friedelan-3ß-yl naproxenate (2b); friedelan-3ß-yl pent-4-ynoate (2c); friedelan-3ß-yl undec-10-ynoate (2d)). Overall, 3α-friedelinol showed greater reactivity when compared to the ß-epimer. The esters 1b-d and 2b-c were tested for antileukemic activity against THP-1 and K-562 cells but showed low cytotoxicity for both cell lines. The most active against THP-1 cells was friedelan-3ß-yl naproxenate (2b, IC50=266±6 µM), and the most active against K-562 cells was friedelan-3α-yl pent-4-ynoate (1c, IC50=267±5 µM).

4.
NanoImpact ; 35: 100517, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38848992

RESUMEN

Superparamagnetic iron oxide nanoparticles (SPIONs) have gained significant attention in biomedical research due to their potential applications. However, little is known about their impact and toxicity on testicular cells. To address this issue, we conducted an in vitro study using primary mouse testicular cells, testis fragments, and sperm to investigate the cytotoxic effects of sodium citrate-coated SPIONs (Cit_SPIONs). Herein, we synthesized and physiochemically characterized the Cit_SPIONs and observed that the sodium citrate diminished the size and improved the stability of nanoparticles in solution during the experimental time. The sodium citrate (measured by thermogravimetry) was biocompatible with testicular cells at the used concentration (3%). Despite these favorable physicochemical properties, the in vitro experiments demonstrated the cytotoxicity of Cit_SPIONs, particularly towards testicular somatic cells and sperm cells. Transmission electron microscopy analysis confirmed that Leydig cells preferentially internalized Cit_SPIONs in the organotypic culture system, which resulted in alterations in their cytoplasmic size. Additionally, we found that Cit_SPIONs exposure had detrimental effects on various parameters of sperm cells, including motility, viability, DNA integrity, mitochondrial activity, lipid peroxidation (LPO), and ROS production. Our findings suggest that testicular somatic cells and sperm cells are highly sensitive and vulnerable to Cit_SPIONs and induced oxidative stress. This study emphasizes the potential toxicity of SPIONs, indicating significant threats to the male reproductive system. Our findings highlight the need for detailed development of iron oxide nanoparticles to enhance reproductive nanosafety.


Asunto(s)
Nanopartículas Magnéticas de Óxido de Hierro , Espermatozoides , Testículo , Masculino , Animales , Ratones , Testículo/efectos de los fármacos , Nanopartículas Magnéticas de Óxido de Hierro/toxicidad , Nanopartículas Magnéticas de Óxido de Hierro/química , Espermatozoides/efectos de los fármacos , Estrés Oxidativo/efectos de los fármacos , Supervivencia Celular/efectos de los fármacos , Células Intersticiales del Testículo/efectos de los fármacos , Células Intersticiales del Testículo/metabolismo , Peroxidación de Lípido/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismo , Citrato de Sodio , Células Cultivadas
5.
Curr Top Med Chem ; 24(18): 1589-1598, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38797894

RESUMEN

INTRODUCTION: Zika virus (ZIKV) is a flavivirus transmitted through the bites of infected Aedes mosquitoes. These viruses can also be transmitted through sexual contact, vertical transmission, and possibly transfusion. Most cases are asymptomatic, but symptoms can include rash, conjunctivitis, fever, and arthralgia, which are characteristic of other arboviruses. Zika infection can lead to complications such as microcephaly, miscarriage, brain abnormalities, and Guillain-Barré syndrome (GBS). OBJECTIVE: The aim is to determine the inhibitory potential of the algae Kappaphycus alvarezii (K. alvarezii) on ZIKV replication. METHODOLOGY: Cytotoxicity experiments were performed using Vero cells to determine the CC50, and ZIKV replication inhibition assays (ATCC® VR-1839™) were conducted to determine the EC50. The mechanism of action was also studied to assess any synergistic effect with Ribavirin. RESULTS: K. alvarezii demonstrated low toxicity with a CC50 of 423 µg/mL and a potent effect on ZIKV replication with an EC50 of 0.65 µg/mL and a Selectivity Index (SI) of 651, indicating the extract's safety. Virucidal effect assays were carried out to evaluate the possible mechanism of action, and the compound addition time was studied, showing the potential to delay the treatment of infected cells by up to 6 hours. A potential synergistic effect was observed when K. alvarezii extract was combined with suboptimal concentrations of Ribavirin, resulting in 99% inhibition of viral replication. CONCLUSION: Our data demonstrate the significant potential of K. alvarezii extract and highlight the need for further studies to investigate its mechanism of action. We propose this extract as a potential anti-Zika compound.


Asunto(s)
Antivirales , Algas Marinas , Replicación Viral , Virus Zika , Antivirales/farmacología , Antivirales/química , Virus Zika/efectos de los fármacos , Animales , Chlorocebus aethiops , Células Vero , Algas Marinas/química , Replicación Viral/efectos de los fármacos , Relación Dosis-Respuesta a Droga , Pruebas de Sensibilidad Microbiana , Relación Estructura-Actividad , Ribavirina/farmacología , Extractos Vegetales/farmacología , Extractos Vegetales/química , Algas Comestibles , Rhodophyta
6.
J Phys Chem Lett ; 15(19): 5243-5249, 2024 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-38718211

RESUMEN

In this work, we provide a general strategy to stabilize the ground state of polyradical(oid)s and make higher spin states thermally accessible. As a proof of concept, we propose to merge two planar fully π-conjugated diradical(oid)s to obtain a planar and cross-conjugated tetraradical(oid). Using multireference quantum chemistry methods, we show that the designed tetraradical(oid) is stabilized by aromaticity and delozalization in the π-system and has six thermally accessible spin states within 1.72 kcal/mol. Analysis of the electronic structure of these six states of the tetraradical(oid) shows that its frontier π-system consists of two weakly interacting subsystems: aromatic cycles and four unpaired electrons. Conjugation between unpaired electrons, which favors closed-shell structures, is mitigated by delocalization and the aromaticity of the bridging groups, leading to the synergistic cross-coupling between two diradical(oid) subunits to stabilize the tetraradical(oid) electronic structure.

7.
Nat Commun ; 15(1): 3070, 2024 Apr 09.
Artículo en Inglés | MEDLINE | ID: mdl-38594249

RESUMEN

Cellular response to redox imbalance is crucial for organismal health. microRNAs are implicated in stress responses. ALG-1, the C. elegans ortholog of human AGO2, plays an essential role in microRNA processing and function. Here we investigated the mechanisms governing ALG-1 expression in C. elegans and the players controlling lifespan and stress resistance downstream of ALG-1. We show that upregulation of ALG-1 is a shared feature in conditions linked to increased longevity (e.g., germline-deficient glp-1 mutants). ALG-1 knockdown reduces lifespan and oxidative stress resistance, while overexpression enhances survival against pro-oxidant agents but not heat or reductive stress. R02D3.7 represses alg-1 expression, impacting oxidative stress resistance at least in part via ALG-1. microRNAs upregulated in glp-1 mutants (miR-87-3p, miR-230-3p, and miR-235-3p) can target genes in the protein disulfide isomerase pathway and protect against oxidative stress. This study unveils a tightly regulated network involving transcription factors and microRNAs which controls organisms' ability to withstand oxidative stress.


Asunto(s)
Proteínas de Caenorhabditis elegans , MicroARNs , Animales , Humanos , Caenorhabditis elegans/genética , Caenorhabditis elegans/metabolismo , Proteínas de Caenorhabditis elegans/metabolismo , MicroARNs/genética , MicroARNs/metabolismo , Estrés Oxidativo/genética , Péptido 1 Similar al Glucagón/metabolismo , Proteínas de Unión al ARN/genética , Proteínas de Unión al ARN/metabolismo
8.
Reprod Toxicol ; 126: 108584, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38561096

RESUMEN

In the domain of medical advancement, nanotechnology plays a pivotal role, especially in the synthesis of biocompatible materials for therapeutic use. Superparamagnetic Iron Oxide Nanoparticles (SPIONs), known for their magnetic properties and low toxicity, stand at the forefront of this innovation. This study explored the reproductive toxicological effects of Sodium Citrate-functionalized SPIONs (Cit_SPIONs) in adult male mice, an area of research that holds significant potential yet remains largely unknown. Our findings reveal that Cit_SPIONs induce notable morphological changes in interstitial cells and the seminiferous epithelium when introduced via intratesticular injection. This observation is critical in understanding the interactions of nanomaterials within reproductive biological systems. A striking feature of this study is the rapid localization of Cit_SPIONs in Leydig cells post-injection, a factor that appears to be closely linked with the observed decrease in steroidogenic activity and testosterone levels. This data suggests a possible application in developing nanostructured therapies targeting androgen-related processes. Over 56 days, these nanoparticles exhibited remarkable biological distribution in testis parenchyma, infiltrating various cells within the tubular and intertubular compartments. While the duration of spermatogenesis remained unchanged, there were many Tunel-positive germ cells, a notable reduction in daily sperm production, and reduced progressive sperm motility in the treated group. These insights not only shed light on the intricate mechanisms of Cit_SPIONs interaction with the male reproductive system but also highlight the potential of nanotechnology in developing advanced biomedical applications.


Asunto(s)
Células Intersticiales del Testículo , Nanopartículas Magnéticas de Óxido de Hierro , Espermatogénesis , Espermatozoides , Testículo , Testosterona , Animales , Masculino , Células Intersticiales del Testículo/efectos de los fármacos , Células Intersticiales del Testículo/metabolismo , Nanopartículas Magnéticas de Óxido de Hierro/toxicidad , Testículo/efectos de los fármacos , Testículo/metabolismo , Espermatogénesis/efectos de los fármacos , Espermatozoides/efectos de los fármacos , Ratones , Citrato de Sodio/toxicidad
9.
Equine Vet J ; 56(4): 697-710, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38567428

RESUMEN

BACKGROUND: Artificial insemination with cooled-shipped semen is the primary method used in the equine breeding industry; yet, sperm quality and fertility can be suboptimal for some stallions when standard techniques are used. Therefore, there is a critical need to develop alternative approaches for these stallions. OBJECTIVE: To assess sperm quality parameters and fertility of cooled-stored stallion semen processed by SpermFilter® or centrifugation and resuspended in three extenders. STUDY DESIGN: Controlled and field study. METHODS: In Experiment 1, semen was collected from 21 stallions classified as having good ('Good-coolers', n = 8) or poor ('Bad-coolers', n = 13) semen cooling. The semen was extended at 30 million spermatozoa/mL in a skimmed milk-based (SM) diluent, and refrigerated for 24 h. Then, the cooled-stored semen was processed through SpermFilter® or centrifugation, and the resulting sperm pellets were resuspended in SM, SM containing pentoxifylline (SM-P), or an egg yolk-based (EY) extender. Unprocessed cooled-stored semen served as control. Sperm motility parameters, plasma membrane integrity (PMI), and mitochondrial membrane potential (HMMP) were assessed in cooled-semen pre- and post-processing. Experiment 2, cooled semen from 9 stallions classified as Bad-coolers was used to inseminate 18 embryo donor mares at 66 cycles (Unprocessed, n = 22; SpermFilter®/SM-P, n = 16; or SpermFilter®/EY, n = 28). Data were analysed with a mixed model and Tukey's as posthoc, and logistic regression. RESULTS: Processed semen resuspended in EY had superior sperm motility compared to unprocessed, SM and SM-P (p < 0.0001). Semen processed by SpermFilter® resuspended in SM-P was similar to EY (p > 0.05). Pellet resuspension with EY and SM-P improved the HMMP of Bad-cooler stallions (p = 0.0010). Semen processed by SpermFilter® had superior PMI to centrifuged semen (p < 0.0001). Mares inseminated with SpermFilter®/SM-P (50%, 8/16) or SpermFilter®/-EY (68%, 9/28) had higher pregnancy rates than mares bred with unprocessed semen (14%, 3/22) (p < 0.001). MAIN LIMITATIONS: Low number of mares in the fertility trial. CONCLUSION: Sperm quality and fertility of Bad-cooler stallions can be enhanced by SpermFilter® and pellet resuspension with either EY or SM-P.


Asunto(s)
Inseminación Artificial , Preservación de Semen , Animales , Caballos/fisiología , Masculino , Preservación de Semen/veterinaria , Preservación de Semen/métodos , Inseminación Artificial/veterinaria , Femenino , Espermatozoides/fisiología , Análisis de Semen/veterinaria , Semen/fisiología , Embarazo , Criopreservación/veterinaria , Criopreservación/métodos , Motilidad Espermática , Frío
10.
ChemistryOpen ; 13(8): e202400030, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38441494

RESUMEN

First synthesized in 1868, alizarin became one of the first synthetic dyes and was widely used as a red dye in the textile industry, making it more affordable and readily available than the traditional red dyes derived from natural sources. Despite extensive both experimental and computational analyses on the electronic effects of substituents on the shape of the visible spectrum of alizarin and alizarin Red S, no previous systematic work has been undertaken with the aim to fine tune the dominant absorption region defining its color by introducing other electron-withdrawing or electron-donor groups. For such, we have performed a comprehensive study of electronic effects of substituents in position C3 of alizarin by means of a time dependent DFT approach. These auxochromes attached to the chromophore are proven to alter both the wavelength and intensity of absorption. It is shown that the introduction of an electron-donor group in alizarin causes the transition bands to be significantly red-shifted whereas electron-withdrawing groups cause a minor blue-shifting.

11.
Chemistry ; 30(27): e202400173, 2024 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-38457260

RESUMEN

The Wittig reaction is one of the most important processes in organic chemistry for the asymmetric synthesis of olefinic compounds. In view of the increasingly acknowledged potentiality of the electric fields in promoting reactions, here we will consider the effect of the oriented external electric field (OEEF) on the second step of Wittig reaction (i. e. the ring opening oxaphosphetane) in a model system for non-stabilized ylides. In particular, we have determined the optimal direction and strength of the electric field that should be applied to annihilate the reaction barrier of the ring opening through the polarizable molecular electric dipole (PMED) model that we have recently developed. We conclude that the application of the optimal external electric field for the oxaphosphetane ring opening favours a Bestmann-like mechanism.

12.
Food Res Int ; 176: 113863, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-38163679

RESUMEN

Yacon is a highly perishable tuberous root, rich in fructooligosaccharides (FOS). Convective drying preceded by ethanol treatment (ET) is an alternative for increasing shelf life in a shorter process. The aim of this study was to investigate the impact of ET and temperature (50 °C and 70 °C) on quality parameters (fructan retention, total phenolic content, antioxidant capacity, shrinkage, color and microstructural parameters) and process parameters (drying time, drying kinetics, and energy consumption) in the convective drying of yacon slices. The ET induced structural alterations in the tissues and cells that aids in the reduction of drying time up to 28.00 %. ET resulted in an increase in effective diffusivity and leaded to noteworthy reduction in energy consumption (up to 22.72 %). The quality parameters such as color, shrinkage, and total phenolic content showed no significant differences among the treatments. The use of ethanol promoted highest preservation of antioxidant activity; however, it caused degradation of FOS. The ethanol pretreated drying at 50 °C was the better condition for lower consumption and preservation of quality parameters as total phenolic content, antioxidant capacity and fructan retention, but the samples dried at 50 °C were the ones with the highest fructan retention (55.11 ± 2.19 %).


Asunto(s)
Antioxidantes , Etanol , Antioxidantes/química , Fenoles/química , Desecación/métodos , Fructanos
13.
J Intensive Care Med ; 39(4): 341-348, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-37769347

RESUMEN

PURPOSE: Bedside transthoracic echocardiography (TTEcho) is a noninvasive cardiac output (CO) monitoring method that has grown recently. However, there are questions regarding its accuracy compared to invasive methods. We aimed to evaluate the agreement and correlation of TTEcho and pulse index continuous CO (PiCCO) monitor measurements for CO and systolic volume (SV) in critically ill patients. METHODS: This prospective experimental study included consecutive adult patients who required invasive hemodynamic monitoring admitted at an intensive care unit in the Federal District, Brazil, from January/2019 to January/2021. Correlation and agreement between SV and CO measurements by PiCCO and TTEcho were performed using the Spearman correlation and the Bland-Altman analysis. RESULTS: The study enrolled 29 patients, with adequate TTEcho evaluations in all patients. There were very strong correlations between CO-TTEcho and CO-PiCCO (r = 0.845, P < .001) and SV-TTEcho and SV-PiCCO (r = 0.800, P < .001). TTEcho estimations for CO and SV were feasible within the limits of agreement in 96.6% (28/29) compared to PiCCO. The mean difference between CO-PiCCO and CO-TTEcho was 0.250 L/min (limits of agreement: -1.083 to 1.583 L/min, percentage error: 21.0%), and between SV-PiCCO and SV-TTEcho was 2.000 mL (limits of agreement: -16.960 to 20.960, percentage error: 24.3%). The reduced cardiac index (CI) measurements by TTEcho showed an accuracy of 89.7% (95% IC: 72.6%-97.8%) and an F1 score of 92.7% (95% IC: 75.0%-98.0%), considering the CI-PiCCO as the gold standard. CONCLUSION: Echocardiographic measurements of CO and SV are comparable to measurements by PiCCO. These results reinforce echocardiography as a reliable tool to evaluate hemodynamics in critically ill patients.


Asunto(s)
Enfermedad Crítica , Ecocardiografía , Adulto , Humanos , Volumen Sistólico , Estudios Prospectivos , Gasto Cardíaco , Monitoreo Fisiológico/métodos
15.
Int J Cardiol ; 395: 131435, 2024 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-37852542

RESUMEN

Doxorubicin (DOXO)-cardiotoxicity is a limiting factor for breast cancer chemotherapy. The relationship between microparticles (MPs) and cardiotoxicity remains unclear. MPs can be released under varying pathophysiological conditions. Thereby, this study aimed to assess MPs derived from cardiomyocytes (CardioMPs), platelets (PMPs) and those that expresses tissue factor (TFMPs) in 80 women with breast cancer undergoing DOXO-based chemotherapy, with or without cardiotoxicity in a one-year follow-up. We observed in the cardiotoxicity group higher count of total-MPs at T0 (prior chemotherapy) (p = 0.034), CardioMPs at T0 and T1 (just after chemotherapy) (p = 0.009 and p = 0.0034) and TFMPs at T0 (p = 0.011) compared to non-cardiotoxicity group. The results suggest that MPs could be associated to cardiotoxicity due to DOXO treatment in breast cancer patients.


Asunto(s)
Neoplasias de la Mama , Cardiotoxicidad , Humanos , Femenino , Cardiotoxicidad/etiología , Neoplasias de la Mama/tratamiento farmacológico , Neoplasias de la Mama/complicaciones , Doxorrubicina/efectos adversos , Miocitos Cardíacos , Tromboplastina
16.
World Allergy Organ J ; 16(12): 100845, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-38075555

RESUMEN

Background: Food allergy has considerably increased in recent years and this situation has been aggravated mainly by the consumption of more processed and complex foods, since minor or potentially allergenic foods are not required to be labeled. Manihot esculenta (cassava) is a widely consumed food in South America, Africa, and Asia and can be used in the production of flour and starch, as well as several other products. This root can cause allergic reactions with symptoms ranging from mild to severe. Methods: Thus, the aim of this study was the characterization of the immunogenic cassava proteins responsible for sensitizing patients allergic to it. Using a 2D-SDS-PAGE based proteomic approach, six proteins were identified, including Fructose Bisphosphate Aldolase (FBA). Recombinant FBA was produced in Expi293 cells and evaluated by immunoblotting with the serum of 10 individual study subjects. Results: Our results showed six cassava IgE-reactive proteins. From those, recombinant fructose bisphosphate aldolase (FBA) showed a positivity of 80% among tested sera, proving to be a highly sensitizing protein. Conclusion: The recombinant FBA molecule obtained in this study can be important for in vivo diagnostic assays, by producing more accurate results, and for desensitization protocols, in which the use of the isolated molecule produces more precise results by avoiding secondary sensitization. Trial registration: All patients signed a consent form approved by the internal ethics committee CAPPesq, Comissão de Ética para Análise de Projetos de Pesquisa do HC FMUSP (CAAE: 10420619.6.0000.0068).

17.
Phys Chem Chem Phys ; 25(45): 31153-31164, 2023 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-37953662

RESUMEN

A systematic computational study is presented aimed at accurately describing the electronic ground state nature and properties of M2C (M = Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W) MXenes. Electronic band structure calculations in the framework of density functional theory (DFT), carried out with different types of basis sets and employing the generalized gradient approach (GGA) and hybrid functionals, provide strong evidence that Ti2C, Zr2C, Hf2C, and Cr2C MXenes exhibit an open-shell conducting ground state with localized spins on the metal atoms, while V2C, Nb2C, Mo2C, Ta2C, and W2C MXenes exhibit a diamagnetic conducting ground state. For Ti2C, Zr2C, Hf2C, and Cr2C, the analysis of the low-lying spin polarized solutions with different spin orderings indicates that their ground states are antiferromagnetic (AFM), consisting of two ferromagnetic (FM) metal layers coupled antiferromagnetically. For the diamagnetic MXenes, the converged spin polarized solutions are significantly less stable than the closed shell solution except for the case of V2C and Mo2C where those excited open shell solutions can be thermally accessible (less than 300 meV per formula unit). The analysis of charge and spin density distributions of the ground state of the MXenes reveals that, in all cases, the metal atoms have a net charge close to +1 e and C atoms close to -2 e. In the case of diamagnetic MXenes, the electronic structure of V2C, Nb2C, and Ta2C is consistent with metal atoms exhibiting a closed-shell s2d2 configuration whereas for Mo2C, and W2C is consistent with a low-spin s1d4 configuration although the FM solution is close in energy for V2C and Mo2C suggesting that they may play a role in their chemistry at high temperature. For the open shell MXenes, the spin density primarily located at the metal atoms showing one unpaired electron per Ti+, Zr+, and Hf+ magnetic center, consistent with s2d1 configuration of the metal atom, and of ∼3.5 unpaired electrons per Cr+ magnetic center interpreted as a mixture of s2d3 and high-spin s1d4 configuration. Finally, the analysis of the density of states reveals the metallic character of all these bare MXenes, irrespective of the nature of the ground state, with significant covalent contributions for Mo2C and W2C.

18.
Foods ; 12(20)2023 Oct 12.
Artículo en Inglés | MEDLINE | ID: mdl-37893645

RESUMEN

The integration of green technologies such as microwave- and enzyme-assisted extraction (MEAE) has been shown to improve the extraction efficiency of bioactive compounds while reducing processing time and costs. MEAE using tannase alone (MEAE-Tan), or in combination with cellulase and pectinase (MEAE-Tan-Cel-Pec), was optimized to produce enriched phenolic and antioxidant extracts from olive pomace. The individual and integrated impact of enzyme concentration, temperature, and pomace/water ratio were determined using a central composite rotatable design. Optimal extraction conditions for MEAE-Tan (60 °C, 15 min, 2.34% of enzyme (w/w), and 1:15 pomace/water ratio) and MEAE-Tan-Cel-Pec (46 °C, 15 min, 2% of enzymes (w/w), in the proportion of 1:1:1, and 1:20 pomace/water ratio) resulted in extracts containing 7110.6 and 2938.25 mg GAE/kg, respectively. The antioxidant activity of the extracts was correlated with phenolic acid release, which was enzyme-dependent, as determined with HPLC-DAD analysis. Enzyme selection had a significant impact on the phenolic profile of extracts, with tannase releasing high concentrations of chlorogenic acid and the combined use of enzymes releasing high concentrations of hydroxytyrosol and chlorogenic and ferulic acids. The novelty of this study relies on the integration and optimization of two green technologies (microwave- and enzyme-assisted extraction) to improve the extraction efficiency of bioactive phenolics from olive pomace while reducing processing time and costs. While these techniques have been evaluated isolated, the benefits of using both processing strategies simultaneously remain largely unexplored. This study demonstrates the effectiveness of the integration and processing optimization of two environmentally friendly technologies as a promising alternative to treat agro-industrial byproducts.

19.
J Agric Food Chem ; 71(42): 15766-15773, 2023 Oct 25.
Artículo en Inglés | MEDLINE | ID: mdl-37843073

RESUMEN

A reliable method using a QuEChERS approach and liquid chromatography coupled to Q-Orbitrap mass spectrometry was optimized and validated for the quantification of 20 growth promoters in bovine serum. The recoveries ranged from 91.4-114.1%, relative standard deviations varied between 0.3-4.0%, and CCα values were between 0.023-0.350 µg L-1. The developed method was applied in an in vivo study using steers, which were intramuscularly treated with commercial injections containing stanozolol. A rapid metabolization was observed, with a detection window ranging from 3 to 10 days. The stability of incurred stanozolol was confirmed after 240 days at -20 °C and also after 5 freeze-thaw cycles. To the best of our knowledge, this is the first work in which an in vivo study was performed to support the monitoring of stanozolol in bovine serum. In addition, the use of Q-Orbitrap high-resolution mass spectrometry allows for retrospective analysis from a surveillance perspective.


Asunto(s)
Estanozolol , Cromatografía Líquida de Alta Presión/métodos , Estudios Retrospectivos , Espectrometría de Masas/métodos , Cromatografía Liquida
20.
Food Res Int ; 173(Pt 2): 113440, 2023 11.
Artículo en Inglés | MEDLINE | ID: mdl-37803766

RESUMEN

Oils and fats are important ingredients for food and pharmaceutical industries. Their main compounds, such as triacylglycerols (TAG), are responsible for determining their physical properties during food storage and consumption. Lipid-rich foods are also sources of minority compounds, which is the case of vitamin E, mainly represented by (±)-α-tocopherol. These compounds can interact with the main lipid molecules in food formulation leading to modification on lipids' physicochemical properties during processes, storage, as well as during digestion, possibly altering their nutritional functionalities, which is the case of vitamin E antioxidant abilities, but also their solubility in the systems. In this case, the study of the phase-behavior between (±)-α-tocopherol and lipid compounds can elucidate these physicochemical changings. Therefore, this work was aimed at determining the solid-liquid equilibrium (SLE) of binary mixtures of TAG (tripalmitin, triolein and tristearin) and (±)-α-tocopherol including the complete description of their phase diagrams. Melting data were evaluated by Differential Scanning Calorimetry, Microscopy, X-Ray Diffraction, and thermodynamic modeling by using Margules, UNIFAC, and COSMO-SAC models. Experimental results showed that systems presented a monotectic-like behavior, with a significant decreasing in TAG melting temperature by the addition of (±)-α-tocopherol. This high affinity and attractive strengths between these molecules were also observed by thermodynamic modeling, whose absolute deviations were below 2 %. Micrographs and X-ray diffraction evidenced the possible formation of solid solutions. Both behaviors are interesting by avoiding phase separation on food in solid and liquid phases, possibly improving the antioxidant role the (±)-α-tocopherol in lipid-base systems.


Asunto(s)
Vitamina E , alfa-Tocoferol , Vitamina E/química , alfa-Tocoferol/química , Antioxidantes , Triglicéridos/química , Temperatura
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