Usefulness of mid-regional proadrenomedullin levels in the resuscitation phase of severely burned patients and its utility in early sepsis detection.

INTRODUCTION: Mid-regional proadrenomedullin (MR-proADM) reflects the adrenomedullin level, which has vasodilatory activity, decreases endothelial permeability, and downregulates proinflammatory cytokines. Sepsis diagnosis in these patients is difficult, and MR-proADM is a widely studied sepsis biomarker. This study evaluates MR-proADM levels during the resuscitation phase, considering the potential influence of haemodynamic changes and its usefulness for the early sepsis detection in burn patients. METHODS: A prospective observational study performed in the Critical Burn Unit. Demographic data, burn characteristics, comorbidities, prognostic/severity scales, and haemodynamic parameters were collected. The resuscitation protocol guided by diuresis, transpulmonary thermodilution, and lactate levels was followed. Blood samples were collected at various time points for biomarker measurement. Biomarker levels, including MR-proADM, C-reactive protein, and procalcitonin were measured during the resuscitation phase and septic episodes. RESULTS: Twenty-seven patients were included, with a mean age of 51 years, a mean total body surface area burn of 41.8%, a mean Abbreviated Burn Severity Index of 9.7, and a mean Baux score of 92. MR-proADM levels were elevated on admission (0.9 ± 0.5 nmol/l) and continued to increase slightly during the resuscitation phase (2.4 ± 2.2 nmol/l). Haemodynamic changes during resuscitation did not significantly affect MR-proADM levels. Twelve of the 27 patients developed sepsis, whose MR-proADM levels were significantly elevated on the day of clinical diagnosis (3.91 ± 2.99 nmol/l) and even the day before (2.57 ± 3.37). Higher MR-proADM levels were associated with greater severity as measured by the Sequential Organ Failure Assessment score. The mean MR-proadrenomedullin values during resuscitation in the patients who died was 3.51 ± 2.30 nmol/l, whereas in the survivors it was 1.28 ± 1.10 nmol/l (p = 0.0001). CONCLUSION: MR-proadrenomedullin values are elevated after thermal injury but are not affected by haemodynamic changes. During septic episodes in burn patients, MR-proADM rises early (the day before sepsis diagnosis). Higher levels of MR-proADM are associated with greater organ dysfunction and mortality.

Sustainable Synthesis of Zeolitic Imidazolate Frameworks at Room Temperature in Water with Exact Zn/Linker Stoichiometry.

Zeolitic imidazolate frameworks (ZIFs) are widely used MOFs because of certain characteristics, but also because they can be prepared at room temperature using water as the unique solvent. However, these a priori sustainable conditions inevitably entail a huge and somehow unusable excess of linker. Here, we present the formation of ZIFs at room temperature in water, starting from mixtures with a linker/metal ratio of two, that is, coinciding with the stoichiometry found in the final MOFs, in the presence of amines. ZIF-8 can be prepared with triethylamine (TEA), giving a yield of Zn of 96.6%. Other bases, like NaOH, tetraethylammonium hydroxide or ammonium hydroxide, do not lead to ZIF-8 under the same conditions. The so-obtained ZIF-8 contains TEA inside its cavities, making it less porous than its conventionally prepared counterparts. Amine can be removed by mild thermal treatments (200-250 °C). Such thermal treatments induce the generation of g-C3N4-like species which could give added value to these materials as potential photocatalysts, increasing their affinity to CO2, as proved in this work. This methodology can be successfully extended to other amines, like N,N-dicyclohexylmethylamine, as well as to other prepared ZIFs, like Co-based ZIF-67, isostructural to ZIF-8.

Metal-organic frameworks for enzyme immobilization and nanozymes: A laccase-focused review.

Laccases are natural catalysts with remarkable catalytic activity. However, their application is limited by their lack of stability. Metal-organic frameworks (MOFs) have emerged as a promising alternative for enzyme immobilization. Enzymes can be immobilized in MOFs via two approaches: postsynthetic immobilization and in situ immobilization. In postsynthetic immobilization, an enzyme is embedded after MOF formation by covalent interactions or adsorption. In contrast, in in situ immobilization, a MOF is formed in the presence of an enzyme. Additionally, MOFs have exhibited intrinsic enzyme-like activity. These materials, known as nanozymes when they have the ability to replace enzymes in certain catalytic processes, have multiple key advantages, such as low cost, easy preparation, and large surface areas. This review presents a general overview of the most recent advances in both enzyme@MOF biocatalysts and MOF-based nanozymes in different applications, with a focus on laccase, which is one of the most widely investigated enzymes with excellent industrial potential.

Preparation and Adsorption Behavior of Ce(III)-MOF for Phosphate and Fluoride Ion Removal from Aqueous Solutions.

The discharge of inorganic pollutants like phosphate and fluoride is a cause of mounting concern to the world due to the substantial environmental and human health risk. Adsorption is one of the most common and affordable technologies widely utilized for removing inorganic pollutants such as phosphate and fluoride anions. Investigating efficient sorbents for the adsorption of these pollutants is extremely important and challenging. This work aimed at studying the adsorption efficiency of the Ce(III)-BDC metal-organic framework (MOF) for the removal of these anions from an aqueous solution using a batch mode. Powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), and scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) techniques evidenced the successful synthesis of Ce(III)-BDC MOF in water as a solvent without any energy input within a short reaction time. The outstanding removal efficiency of phosphate and fluoride was exhibited at an optimized pH (3, 4), adsorbent dose (0.20, 0.35 g), contact time (3, 6 h), agitation speed (120, 100 rpm), and concentration (10, 15 ppm) for each ion, respectively. The experiment on the effect of coexisting ions demonstrated that SO42- and PO43- ions are the primary interfering ions in phosphate and fluoride adsorption, respectively, while the HCO3- and Cl- ions were found to have interfered less. Furthermore, the isotherm experiment showed that the equilibrium data fitted well with the Langmuir isotherm model and the kinetic data correlated well with the pseudo-second-order model for both ions. The results of thermodynamic parameters such as ΔH°, ΔG°, and ΔS° evidenced an endothermic and spontaneous process. The regeneration of the adsorbent made using water and NaOH solution showed the easy regeneration of the sorbent Ce(III)-BDC MOF, which can be reused four times, revealing its potential application for the removal of these anions from aqueous environment.

Trastornos circadianos del sueño / Circadian Sleep Disorders

Resumen El sistema circadiano está sincronizado al ciclo luz-oscuridad que es generado por la rotación de la tierra, asegurando que la vigilia sea durante el día y que el sueño ocurra durante la noche. Sin embargo, el ritmo de sueño-vigilia puede estar desincronizado del ciclo luz-oscuridad o desincronizado de manera endógena, dando como resultado: insomnio, fatiga y bajo rendimiento en las actividades cotidianas. Mientras que los trastornos del sueño están clasificados por la Asociación Americana de Trastornos del Sueño como: disomnias intrínsecas, disomnias extrínsecas, parasomnias o trastornos del sueño médicos/psiquiátricos. Los trastornos circadianos del sueño se han categorizado por separado, en parte para reconocer que en la mayoría de los casos la etiología de los trastornos circadianos es una mezcla de factores internos y ambientales, o por un desajuste temporal entre ambos. Los síntomas generalmente son insomnio o hipersomnia, síntomas comunes en pacientes con trastornos circadianos del sueño, aunque hay otras causas a las que pueden atribuirse y que deben excluirse antes de realizar el diagnóstico de un trastorno circadiano del sueño. En el paciente sin otra patología del sueño, un registro diario de actividades, comidas, ejercicio, siestas y la hora de acostarse es una herramienta esencial para evaluar los trastornos circadianos del sueño. Estos registros deben mantenerse durante 2 semanas o más, ya que una perturbación debida a cambios de trabajo o viajes a través de zonas horarias puede tener efectos sobre el sueño y el estado de alerta durante el día, semanas después del evento.

Abstract The circadian system is synchronized to the light-dark cycle generated by the rotation of the earth, ensuring that wakefulness is during the day and sleep occurs at night. However, the sleep-wake rhythm may be out of sync with the light-dark cycle or endogenously out of sync, resulting in insomnia, fatigue, and poor performance in activities of daily living. Sleep disorders are classified by the American Sleep Disorders Association, as intrinsic dyssomnias, extrinsic dyssomnias, parasomnias, or medical/psychiatric sleep disorders. Circadian sleep disorders have been categorized separately to recognize that in most cases the etiology of circadian disturbances is a mix of internal and environmental factors or a temporary mismatch between the two. Symptoms are usually insomnia or hypersomnia, common symptoms in patients with circadian sleep disorders although other causes can be attributed and must be excluded before a diagnosis of a circadian sleep disorder is made. In the patient without other sleep pathology, a daily record of activities, meals, exercise, naps, and bedtime is an essential tool in assessing circadian sleep disorders. These records should be kept for 2 weeks or more, as a disturbance due to job changes or travel across time zones can have effects on sleep and daytime alertness weeks after the event.

Bromelain-based enzymatic burn debridement: Spanish multidisciplinary consensus.

Background: Bromelain-based enzymatic debridement is gaining increased interest from burn specialists in the last few years. The objective of this manuscript is to update the previous, first Spanish consensus document from 2017 (Martínez-Méndez et al. 43:193-202, 2017), on the use of enzymatic debridement with NexoBrid® in burn injuries, adding the clinical experience of a larger panel of experts, integrating plastic surgeons, intensivists, and anesthesiologists. Methods: A consensus guideline was established by following a modified Delphi methodology of a 38-topic survey in two rounds of participation. Items were grouped in six domains: general indication, indication in critical patients, pain management, conditions for NexoBrid® application, NexoBrid® application technique, and post-debridement wound care. Results: In the first round, experts established consensus (strongly agree or agree) on 13 of the 38 statements. After the second round, a consensus was reached on 24 of the 25 remaining statements (97.2%). Conclusions: The present updated consensus document provides recommendations on the use of bromelain-based enzymatic debridement NexoBrid®, integrating the extensive clinical experience of plastic surgeons, intensivists, and anesthesiologists in Spain. Further clinical trials and studies are required to corroborate, modify, or fine tune the current statements.

Effect of a light-darkness cycle on the body weight gain of preterm infants admitted to the neonatal intensive care unit.

The Continuous bright light conditions to which premature infants are subjected while hospitalized in Neonatal Intensive Care Units (NICU) can have deleterious effects in terms of growth and development. This study evaluates the benefits of a light/darkness cycle (LDC) in weight and early hospital discharge from the NICU. Subjects were recruited from three participating institutions in Mexico. Eligible patients (n = 294) were premature infants who were hospitalized in the low-risk and high-risk neonatal units classified as stable. The subjects randomized to the experimental group (n = 150) were allocated to LDC conditions are as follows: light from 07:00 to 19:00 and darkness (25 lx) from 19:00 to 07:00. The control group (n = 144) was kept under normal room light conditions (CBL) 24 h a day. Main outcome was weight gain and the effect of reducing the intensity of nocturnal light in development of premature infants. Infants to the LDC gained weight earlier, compared with those randomized to CBL, and had a significant reduction in length of hospital stay. These results highlight those premature infants subjected to a LDC exhibit improvements in physiological development, favoring earlier weight gain and consequently a decrease in hospital stays. ClinicalTrials.gov; 02/09/2020 ID: NCT05230706.

High Dose Ascorbic Acid During Acute Resuscitation in Critically Burn Patients.

Ascorbic acid (AA) is a potent oxygen-free radical scavenger. We hypothesized that treating severe burn patients with high doses of AA (HDAA) can reduce fluid resuscitation requirements and prevent organ dysfunction. We performed a unicentric, retrospective case-control study of 75 burn patients: 25 patients admitted from 2018 to 2019 with more than 30% Total Surface Body Surface Area (TSBA) burned who received HDAA (66 mg/kg/h as soon as possible after admission until 36 h after injury), and 50 patients admitted from 2014 to 2017 with similar Abbreviated Burn Severity Index (ABSI)/Baux scores who were treated with the same protocol but did not receive HDAA. During the first 24 hours of burn resuscitation the HDAA group required less fluids than the control group (3.06 ± 0.87 ml/kg/%TBSA vs 4.32 ± 1.51 P < .05), but the overall reduction of fluid requirements during the first 72 hours was not significant. There were no significant differences in Sequential Organ Failure Assessment (SOFA), other hemodynamic parameters, complications, or mortality. We also did not find an increase acute kidney injury in patients who received HDAA even though the mean urine oxalate/creatinine ratio was 0.61 (0.02-0.96). We conclude that in severe burn patients treated with a restrictive fluid therapy protocol, administration of HDAA can decrease only the initial fluid requirements but not total fluid intakes. We did not find differences in severity score after resuscitation or in mortality. Nor did we find an increase in renal failure in patients administered with HDAA.

Efficacy and safety of early target-controlled plasma volume replacement with a balanced gelatine solution versus a balanced electrolyte solution in patients with severe sepsis/septic shock: study protocol, design, and rationale of a prospective, randomized, controlled, double-blind, multicentric, international clinical trial : GENIUS-Gelatine use in ICU and sepsis.

BACKGROUND: Sepsis is associated with capillary leakage and vasodilatation and leads to hypotension and tissue hypoperfusion. Early plasma volume replacement is required to achieve haemodynamic stability (HDS) and maintain adequate tissue oxygenation. The right choice of fluids to be used for plasma volume replacement (colloid or crystalloid solutions) is still a matter of debate, and large trials investigating the use of colloid solutions containing gelatine are missing. This study aims to investigate the efficacy and safety of plasma volume replacement using either a combined gelatine-crystalloid regime (1:1 ratio) or a pure crystalloid regime. METHODS: This is a prospective, controlled, randomized, double-blind, international, multicentric phase IV study with two parallel groups that is planned to be conducted at European intensive care units (ICUs) in a population of patients with hypovolaemia in severe sepsis/septic shock. A total of 608 eligible patients will be randomly assigned to receive either a gelatine-crystalloid regime (Gelaspan® 4% and Sterofundin® ISO, B. Braun Melsungen AG, in a 1:1 ratio) or a pure crystalloid regime (Sterofundin® ISO) for plasma volume replacement. The primary outcome is defined as the time needed to achieve HDS. Plasma volume replacement will be target-controlled, i.e. fluids will only be administered to volume-responsive patients. Volume responsiveness will be assessed through passive leg raising or fluid challenges. The safety and efficacy of both regimens will be assessed daily for 28 days or until ICU discharge (whichever occurs first) as the secondary outcomes of this study. Follow-up visits/calls will be scheduled on day 28 and day 90. DISCUSSION: This study aims to generate evidence regarding which regimen-a gelatine-crystalloid regimen or a pure crystalloid regimen-is more effective in achieving HDS in critically ill patients with hypovolaemia. Study participants in both groups will benefit from the increased safety of target-controlled plasma volume replacement, which prevents fluid administration to already haemodynamically stable patients and reduces the risk of harmful fluid overload. TRIAL REGISTRATION: The European clinical trial database EudraCT 2015-000057-20 and the ClinicalTrials.gov Protocol Registration and Results System ClinicalTrials.gov NCT02715466 . Registered on 17 March 2016.

Lesión axonal difusa asociada a infección por COVID-19 / Diffuse axonal injury associated with COVID-19 infection

No disponible

Lactate and lactate clearance in critically burned patients: usefulness and limitations as a resuscitation guide and as a prognostic factor.

OBJECTIVE: Lactate levels to guide resuscitation in critically burned patients are controversial. The purpose of our study was to determine whether absolute lactate values or lower lactate clearance predict mortality, and whether these are useful tools in the resuscitation phase. METHODS: We conducted a prospective, unicentric, observational study of a cohort of 214 burn patients admitted in the Burn Intensive Care Unit. We collected demographic and laboratory data, complications, absolute lactate levels and lactate clearance every 8 h since admission to 72 h. In critical patients we monitored hemodynamic parameters with transpulmonary thermodilution. We used Student's t-test or nonparametric tests, mixed models and Pearson and Spearman methods, Fisher's exact and chi-squared test. RESULTS: Of the 214 patients, 76.6% were male, mean age were 46 ± 15 years and 23.0 ± 19.5% of Total Basal Surface Area (TBSA) burned. Initial mean absolute levels of lactate were 2.02 ± 1.62 mmol/L in survivors vs. 4.05 ± 3.90 mmol/L in nonsurvivors. Initial elevated lactate levels increased mortality (p < .001), length of ICU stay, mechanical ventilation and shock. In the subgroup of burned TBSA < 20%, lowering the lactate cut-off point from 2.0 to 1.8 mmol/L improved the mortality prediction (OR:9.3). We found no relationship between lactate clearance in the first 24 h and mortality. In more severe patients (> 20% TBSA burned and initial lactate levels > 2), a good correlation was found between lactate and cardiac index; but not with intrathoracic blood volume index (ITBVI). Patients with low ITBVI preload (< 600 mL/m2) did not show significant differences in lactate clearance compared with those with ITBVI > 600. CONCLUSIONS: Initial elevated lactate levels are a factor of poor prognosis and the cut-off point that best predicts mortality should be adjusted in the patients with TBSA burned < 20%. The global clearance of lactate in the first 24 h, unlike what occurs in other injuries, does not correlate with mortality. Monitoring lactate can ensure adequate peripheral perfusion during resuscitation with lower than normal fluid preload values.

Perspectiva quirúrgica de los resultados del desbridamiento enzimático en grandes quemados / Surgical perspective of enzymatic debridement outcomes in major burns

INTRODUCCIÓN Y OBJETIVO: El desbridamiento enzimático ha demostrado ser eficaz y rápido en su aplicación sobre quemaduras, a la vez que conservador con el tejido sano. Su uso sobre quemaduras inferiores al 15% ha mostrado reducir la cantidad de injertos, el sangrado y las escarotomías quirúrgicas. El objetivo de este estudio es comparar 2 grupos de pacientes grandes quemados, uno tratado mediante desbridamiento enzimático frente a otro tratado mediante tratamiento estándar, y su impacto en la estancia hospitalaria, necesidades de escarotomías, tiempo hasta desbridamiento, uso de hemoderivados y cantidad de cirugías durante el ingreso. MATERIAL Y MÉTODO: Estudio de cohortes retrospectivas con 197 pacientes (SCQ 20-50%), mayores de 18 años, tratados entre 2012 y 2017, con 2 grupos: 32 pacientes tratados con Nexobrid® para el desbridamiento enzimático, y 165 pacientes en el grupo control con desbridamiento tangencial convencional. Ambos homogéneos para SCQ, edad, sexo, mecanismo de lesión y comorbilidades. RESULTADOS: La edad media fue de 48.4 ± 19.4 años, con una SCQ media de 29.5 ± 9.4%. Observamos disminución del tiempo hasta el inicio del desbridamiento de la quemadura (5.1 ± 4.9 días en el grupo control frente a 0.8±0.9 en el grupo de desbridamiento enzimático, p < 0.05). El grupo de Nexobrid® presentó una reducción de la cantidad de tiempos quirúrgicos durante su ingreso, siendo de 1.9±2.0 frente a 2.6±2.1 en el grupo control. El uso de hemoderivados se redujo en un 95% durante el desbridamiento. La necesidad de escarotomías se redujo un 60%. Finalmente, el grupo de Nexobrid® tuvo un 36% menos de estancia en la Unidad de Quemados Críticos, con diferencias estadísticamente significativas. CONCLUSIONES: La aplicación precoz del desbridamiento enzimático en grandes quemados (20-50% SCQ), permite la escarectomía completa del paciente reduciendo la necesidad de hemoderivados, el número de tiempos quirúrgicos, las escarotomías y la estancia en la unidad de cuidados intensivos

BACKGROUND AND OBJECTIVE: Use of enzymatic debridement has demonstrated be fast and efficient after its application over burn wounds, being more delicate over healthy tissue. Its use in burns under 15% TBSA has shown less grafting procedures, bleeding and surgical escharotomies. The aim of this study was compare 2 groups of major burns; one treated by enzymatic debridement and other treated by standard of care. Length of stay, escharotomies, time until debridement, use of blood packs and number of surgeries during hospitalization were evaluated. METHODS: A retrospective cohort study was designed with 197 patients (TBSA 20-50%), older than 18 years old, treated between 2012 and 2017, and divided in 2 groups: 32 patients were debrided using Nexobrid®, and 165 patients were included in the control group. Both groups were homogeneous for TBSA, age, gender, mechanism and comorbidities index. RESULTS: Mean age was 48.4±19.4 years, with a 29.5±9.4% of TBSA. A reduction of the number of days until the burns debridement were found, with 5.1±4.9 in the control group and 0.8±0.9 days in the enzymatic debridement group (p < 0.05). The number of surgeries during the hospitalization were less in the Nexobrid® group, with a reduction of 2.6±2.1 surgeries to 1.9±2.0. The number of blood packs was a 95% lower in the enzymatic debridement, and a 60% less escharotomies were observed. Finally, a shorter length of stay in the intensive care unit were found in the Nexobrid® group, with 36% less days, this difference were statistically significant. CONCLUSIONS: Early application of enzymatic debridement in major burns (20-50% TBSA) allows a complete removal of eschar reducing the blood packs use, number of surgeries, escharotomies and length of stay in the intensive care unit

Environmentally Friendly Enzyme Immobilization on MOF Materials.

Metal-organic framework (MOF) materials have revolutionized the applications of nanoporous materials. They can be potentially used in separation, storage, and catalysis, among other applications. Since their discovery in 1999 (Li et al. Nature 402:276-279, 1999; Chui Science 283:1148-1150, 1999), more than 20,000 new structures have been synthesized thanks in part to their high compositional versatility. However, only some of them are really stable in water (both in liquid and vapor phase), which limits their employment in other applications. Furthermore, biocatalysis field has been demanding a "universal support" able to encapsulate/immobilize any type of enzyme in a straightforward methodology and, simultaneously, capable of keeping the enzymatic catalytic activity. This requisite set has been a big challenge considering the drastic synthesis conditions required for most of the MOF materials. Thus, a compromise between the development of a well-formed material support and an acceptable enzymatic activity had to be achieved in order to obtain active biocatalysts, ideally prepared in just one step and under sustainable conditions. In this chapter, we describe the protocols about how to synthesize MOF materials in water, under mild conditions and almost instantaneously in the presence of enzymes. The most successful support of these sustainable MOFs was the semicrystalline Fe-BTC MOF material (like the commercial Basolite F300) allowing the development of efficient active biocatalysts (97% with respect to the free enzyme in the case of CALB lipase). Particularly, this enzyme support improves the benefits given by some other MOF-based supports also described in this chapter, like NH2-MIL-53(Al). Furthermore, we present the post-synthesis immobilization approach, which consists firstly in the synthesis or preparation of the respective MOF material (Fe-BTC or NH2-MIL-53(Al)), followed by an enzyme immobilization protocol. As reported in bibliography, MOFs as enzyme supports combine together more active biocatalysts with lower enzyme leaching when compared to other conventional materials. Moreover, MOFs prepared in non-aqueous media (for instance, N,N-dimethylformamide) can also trap enzymes in an otherwise adverse media. These facts bring these biocatalysts closer to industrial employment in even more demanding applications.

Observation of Ag Nanoparticles in/on Ag@MIL-100(Fe) Prepared Through Different Procedures.

Loading of active metals, metal clusters, and/or metal nanoparticles in Metal Organic Frameworks (MOFs) is an emergent field with applications in sensors, catalysis, medicine, and even in the polymeric industry. In the present work, MIL-100(Fe) has been synthesized and reacted with AgNO3 through liquid and incipient wetness, and also through solid-state reaction or solid grinding. The aim of this study is to evaluate whether the MIL-100 would uptake metal particles using a similar principle as that of the ion exchange in zeolites, or else, their inherent humidity would favor the "dissolution" of the metal salt, thus yielding very small metal particles. The immobilization of Ag nanoparticles inside the MOF pores was identified by Cs-corrected scanning transmission electron microscopy (Cs-corrected STEM) techniques.

Greener synthesis of Cu-MOF-74 and its catalytic use for the generation of vanillin.

A greener synthesis of Cu-MOF-74 was obtained, for the first time, in methanol as the unique solvent and at room temperature. Full characterisation of the MOF material showed its purity and also its nanocrystalline nature. Complete activation (150 °C for 1 h and 10-3 bar) of Cu-MOF-74 afforded unsaturated Cu metal sites and this was corroborated by in situ DRIFT spectroscopy. The access to these Cu open metal sites was tested for the catalytic transformation of trans-ferulic acid to vanillin (yield of 71% and 97% selectivity) and a plausible catalytic reaction mechanism was postulated based on quantum chemical calculations.

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.