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To use natural gas as a feedstock alternative to coal and oil, its main constituent, methane, needs to be isolated with high purity1. In particular, nitrogen dilutes the heating value of natural gas and is, therefore, of prime importance for removal2. However, the inertness of nitrogen and its similarities to methane in terms of kinetic size, polarizability and boiling point pose particular challenges for the development of energy-efficient nitrogen-removing processes3. Here we report a mixed-linker metal-organic framework (MOF) membrane based on fumarate (fum) and mesaconate (mes) linkers, Zr-fum67-mes33-fcu-MOF, with a pore aperture shape specific for effective nitrogen removal from natural gas. The deliberate introduction of asymmetry in the parent trefoil-shaped pore aperture induces a shape irregularity, blocking the transport of tetrahedral methane while allowing linear nitrogen to permeate. Zr-fum67-mes33-fcu-MOF membranes exhibit record-high nitrogen/methane selectivity and nitrogen permeance under practical pressures up to 50 bar, removing both carbon dioxide and nitrogen from natural gas. Techno-economic analysis shows that our membranes offer the potential to reduce methane purification costs by about 66% for nitrogen rejection and about 73% for simultaneous removal of carbon dioxide and nitrogen, relative to cryogenic distillation and amine-based carbon dioxide capture.
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OBJECTIVE: To evaluate tiragolumab (anti-TIGIT) and atezolizumab (anti-PD-L1) as second- or third-line therapy for PD-L1-positive persistent/recurrent cervical cancer. METHODS: In the open-label, non-comparative, randomized phase II SKYSCRAPER-04 trial (NCT04300647), patients with PD-L1-positive (SP263 tumor area positivity ≥5%) recurrent/persistent cervical cancer after 1-2 chemotherapy lines (≥1 platinum-based) were randomized 3:1 to atezolizumab 1200 mg with/without tiragolumab 600 mg every 3 weeks until disease progression or unacceptable toxicity. Stratification factors were performance status, prior (chemo)radiotherapy, and disease status. The primary endpoint was independent review committee-assessed confirmed objective response rate per RECIST v1.1 in patients receiving tiragolumab plus atezolizumab. An objective response rate ≥21% (one-sample z-test p≤0.0245) was required for statistical significance versus a historical reference. RESULTS: Protocol-defined independent review committee-assessed objective response rates were 19.0% (95% CI 12.6 to 27.0) in 126 patients receiving tiragolumab plus atezolizumab (p=0.0787 vs historical reference) and 15.6% (95% CI 6.5 to 29.5) in 45 atezolizumab-treated patients. Response rates were higher in PD-L1high (tumor area positivity ≥10%) than PD-L1low (tumor area positivity 5%-9%) subgroups with both regimens. At 8.5 months' median follow-up, independent review committee-assessed progression-free survival was 2.8 months (95% CI 1.7 to 4.1) with tiragolumab plus atezolizumab and 1.9 months (95% CI 1.5 to 3.0) with atezolizumab. In post hoc analyses (10.4 months' median follow-up), median overall survival was 11.1 months (95% CI 9.6 to 14.5) with the combination and 10.6 months (95% CI 6.9 to 13.8) with atezolizumab (crossover permitted). In the combination group, 3% of patients had adverse events requiring treatment discontinuation and 8% had grade ≥3 adverse events of special interest; corresponding values in the single-agent arm were 4% and 11%. There were no treatment-related deaths or new safety findings. CONCLUSION: The objective response rate with the tiragolumab-plus-atezolizumab combination was numerically higher than the historical reference but did not reach statistical significance.
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Anticuerpos Monoclonales Humanizados , Recurrencia Local de Neoplasia , Neoplasias del Cuello Uterino , Humanos , Femenino , Neoplasias del Cuello Uterino/tratamiento farmacológico , Neoplasias del Cuello Uterino/patología , Anticuerpos Monoclonales Humanizados/administración & dosificación , Persona de Mediana Edad , Recurrencia Local de Neoplasia/tratamiento farmacológico , Recurrencia Local de Neoplasia/patología , Adulto , Anciano , Antígeno B7-H1/metabolismo , Antígeno B7-H1/antagonistas & inhibidores , Protocolos de Quimioterapia Combinada Antineoplásica/uso terapéuticoRESUMEN
The nonpsychoactive cannabinoid, cannabidiol (CBD), is Food and Dug Administration approved for treatment of two drug-resistant epileptic disorders and is seeing increased use among the general public, yet the mechanisms that underlie its therapeutic effects and side-effect profiles remain unclear. Here, we report a systems-level analysis of CBD action in human cell lines using temporal multiomic profiling. FRET-based biosensor screening revealed that CBD elicits a sharp rise in cytosolic calcium, and activation of AMP-activated protein kinase in human keratinocyte and neuroblastoma cell lines. CBD treatment leads to alterations in the abundance of metabolites, mRNA transcripts, and proteins associated with activation of cholesterol biosynthesis, transport, and storage. We found that CBD rapidly incorporates into cellular membranes, alters cholesterol accessibility, and disrupts cholesterol-dependent membrane properties. Sustained treatment with high concentrations of CBD induces apoptosis in a dose-dependent manner. CBD-induced apoptosis is rescued by inhibition of cholesterol synthesis and potentiated by compounds that disrupt cholesterol trafficking and storage. Our data point to a pharmacological interaction of CBD with cholesterol homeostasis pathways, with potential implications in its therapeutic use.
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Cannabidiol , Cannabinoides , Humanos , Cannabidiol/farmacología , Calcio/metabolismo , Proteínas Quinasas Activadas por AMP , Línea Celular , Cannabinoides/farmacología , Homeostasis , ARN Mensajero/metabolismo , ColesterolRESUMEN
The Catalysis Hub - Swiss CAT+ is a new infrastructure project funded by ETH-domain, co-headed by EPFL and ETHZ. It offers the scientific community a unique integrated technology platform combining automated and high-throughput experimentation with advanced computational data analysis to accelerate the discoveries in the field of sustainable catalytic technologies. Divided into two hubs of expertise, homogeneous catalysis at EPFL and heterogeneous catalysis at ETHZ, the platform is open to academic and private research groups. Following a multi-year investment plan, both hubs have acquired and developed several high-end robotic platforms devoted to the synthesis, characterization, and testing of large numbers of molecular and solid catalysts. The hardware is associated with a fully digitalized experimental workflow and a specific data management strategy to support closed-loop experimentation and advanced computational data analysis.
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More than 95% (in volume) of all of today's chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic research field. In this regard, metal-organic frameworks (MOFs) offer great opportunities for the rational design of new catalytic solids, as highlighted by the unprecedented number of publications appearing over the past decade. In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed. MOFs with intrinsic thermocatalytic activity, as hosts for the incorporation of metal nanoparticles, as precursors for the manufacture of composite catalysts and those active in photo- and electrocatalytic processes are critically reviewed. The review is wrapped up with our personal view on future research directions.
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PURPOSE: Mental health disparities have been documented among sexual minority college students, but there is a dearth of evidence from developing countries. The aim is to estimate the prevalence of 12-month mental and substance use disorders across a range of sexual identities among first-year college students in Mexican universities, and test whether there is an association between sexual identity and disorders and whether the association is moderated by gender. METHOD: The University Project for Healthy Students, a web-based survey conducted as part of the World Health Organization's World Mental Health International College Student initiative, recruited 7874 students from nine Mexican universities in 2016 and 2017. Logistic regressions estimated the association of sexual identity with 12-month major depressive episode, generalized anxiety disorder, panic disorder, alcohol abuse/dependence, and drug abuse/dependence, with interaction terms for gender. RESULTS: Compared to heterosexual students reporting no same-sex attraction (SSA), heterosexual students with SSA (AORs range 1.77-3.67) and lesbian/gay and bisexual students (AORs range 2.22-5.32) were at a higher risk for several disorders. Asexual students were at higher risk for drug abuse/dependence (AOR = 3.64). Students unsure of their sexual identity were at a higher risk for major depressive episode, panic disorder, and drug abuse/dependence (AORs range 2.25-3.82). Gender differences varied across sexual identity and disorder. CONCLUSION: These findings are the first empirical report of sexual minority psychiatric disparities among a college student population from a developing nation and underscore the importance of clinical interventions that address mental health needs among sexual minority college students.
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Trastorno Depresivo Mayor , Trastornos Mentales , Minorías Sexuales y de Género , Trastornos Relacionados con Sustancias , Trastorno Depresivo Mayor/epidemiología , Femenino , Humanos , Trastornos Mentales/epidemiología , México/epidemiología , Prevalencia , Estudiantes , Trastornos Relacionados con Sustancias/epidemiología , UniversidadesRESUMEN
This article is on fast-consensus reaching in a class of multi-agent systems (MAS). We present an analytical approach to tune controllers for the agents based on the premise that delayed measurements in the controller can be preferable to standard controllers relying only on current measurements. Controller tuning in this setting is however challenging due to the presence of delays. To tackle this problem, we propose an analytic geometry approach. The key contribution is that the tuning can be implemented for complex eigenvalues of the arising graph Laplacian of the network, complementing the current state of the art, which is limited to real eigenvalues. Results, therefore, extend our knowledge beyond symmetric graphs and enable the study of the MAS under directed graphs. This article is part of the theme issue 'Nonlinear dynamics of delay systems'.
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OBJECTIVE: To estimate psychopathology and self-harm behavior of incoming first-year college students, sociodemographic correlates, service use and willingness to seek treatment. MATERIALS AND METHODS: 4 189 male and female incoming first-year students of six universities in four different states of Mexico responded to an online survey with a 79.3% response rate. RESULTS: Almost one in three incoming students has experienced some type of psychopathology; however, only one in five has received treatment. Female, students who are older, whose parents are not married or deceased, and who have a non-heterosexual orientation, no religion or a non-Catholic/Christian religion have greater odds (1.18 - 1.99), whereas those who attend a private university and have a parent with some college education have lower odds (0.68 - 0.75) of experiencing any probable disorder. CONCLUSIONS: Substantial unmet need for mental health services combined with reported willingness to use university services suggests an opportunity for the detection, referral, and treatment of incoming students to promote a successful transition.
OBJETIVO: Estimar psicopatologías y autolesiones en universitarios de nuevo ingreso, así como los correlatos sociodemográficos, el uso de servicios y la disposición para recibir tratamiento. MATERIAL Y MÉTODOS: 4 189 estudiantes de nuevo ingreso de seis universidades en cuatro estados contestaron una encuesta en línea con una tasa de respuesta de 79.3%. RESULTADOS: 32.5% han padecido psicopatologías en su vida, pero únicamente 19.5% han recibido tratamiento. Mujeres, estudiantes con una orientación no heterosexual, estudiantes de mayor edad, quienes tienen padres fallecidos o no casados, sin religión o con una religión no católica/cristiana tienen mayor probabilidad de presentar psicopatologías (RM= 1.18-1.99), mientras que aquellos de universidades privadas y cuyos padres tienen estudios universitarios tienen menor probabilidad (RM= 0.68-0.75). CONCLUSIONES: La alta tasa de psicopatologías no tratadas combinada con la disposición reportada de recibir servicios a través de su universidad sugiere una oportunidad para la detección, canalización y tratamiento de alumnos de nuevo ingreso para promover una transición exitosa.
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Trastornos Mentales/epidemiología , Conducta Autodestructiva/epidemiología , Estudiantes/psicología , Trastornos Relacionados con Sustancias/epidemiología , Adolescente , Adulto , Femenino , Necesidades y Demandas de Servicios de Salud , Encuestas Epidemiológicas , Humanos , Masculino , Trastornos Mentales/psicología , Trastornos Mentales/terapia , Servicios de Salud Mental/provisión & distribución , México/epidemiología , Prevalencia , Conducta Autodestructiva/psicología , Distribución por Sexo , Factores Socioeconómicos , Estudiantes/estadística & datos numéricos , Trastornos Relacionados con Sustancias/psicología , Trastornos Relacionados con Sustancias/terapia , Ideación Suicida , Intento de Suicidio/estadística & datos numéricos , Universidades , Adulto JovenRESUMEN
Sorafenib (Nexavar) is a broad-spectrum multikinase inhibitor that proves effective in treating advanced renal-cell carcinoma and liver cancer. Despite its well-characterized mechanism of action on several established cancer-related protein kinases, sorafenib causes variable responses among human tumors, although the cause for this variation is unknown. In an unbiased screening of an oncology drug library, we found that sorafenib activates recruitment of the ubiquitin E3 ligase Parkin to damaged mitochondria. We show that sorafenib inhibits the activity of both complex II/III of the electron transport chain and ATP synthase. Dual inhibition of these complexes, but not inhibition of each individual complex, stabilizes the serine-threonine protein kinase PINK1 on the mitochondrial outer membrane and activates Parkin. Unlike the protonophore carbonyl cyanide m-chlorophenylhydrazone, which activates the mitophagy response, sorafenib treatment triggers PINK1/Parkin-dependent cellular apoptosis, which is attenuated upon Bcl-2 overexpression. In summary, our results reveal a new mechanism of action for sorafenib as a mitocan and suggest that high Parkin activity levels could make tumor cells more sensitive to sorafenib's actions, providing one possible explanation why Parkin may be a tumor suppressor gene. These insights could be useful in developing new rationally designed combination therapies with sorafenib.
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Complejo III de Transporte de Electrones/antagonistas & inhibidores , Complejo II de Transporte de Electrones/antagonistas & inhibidores , Mitocondrias/efectos de los fármacos , ATPasas de Translocación de Protón Mitocondriales/antagonistas & inhibidores , Niacinamida/análogos & derivados , Compuestos de Fenilurea/farmacología , Proteínas Quinasas/metabolismo , Ubiquitina-Proteína Ligasas/metabolismo , Células Cultivadas , Transporte de Electrón/efectos de los fármacos , Complejo II de Transporte de Electrones/metabolismo , Complejo III de Transporte de Electrones/metabolismo , Células HEK293 , Humanos , Mitocondrias/enzimología , Mitocondrias/metabolismo , ATPasas de Translocación de Protón Mitocondriales/metabolismo , Niacinamida/farmacología , SorafenibRESUMEN
A series of isomeric phenylphenalenones in which the phenyl ring is located at all possible peripheral positions of the phenalenone nuclei was synthesized. The structural characteristics of the series, in which topological variation is permitted with minimal electronic disturbance, could, in principle, allow for easy pharmacophore recognition when the compounds are aligned in steroidomimetic conformations.
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The selective oxidation of ethylene to ethylene epoxide is highly challenging as a result of competing reaction pathways leading to the deep oxidation of both ethylene and ethylene oxide. Herein we present a novel catalyst based on silver and copper oxide with an excellent response in the selective oxidation pathway towards ethylene epoxide. The catalyst is composed of different silver nanostructures dispersed on a tubular copper oxide matrix. This type of hybrid nanoarchitecture seems to facilitate the accommodation of chlorine promoters, leading to high yields at low reaction temperatures. The stability after the addition of chlorine promoters implies a substantial improvement over the industrial practice: a single pretreatment step at ambient pressure suffices in contrast with the common practice of continuously feeding organochlorinated precursors during the reaction.
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The PTEN-induced kinase 1 (PINK1)-Parkin pathway plays a vital role in maintaining a healthy pool of mitochondria in higher eukaryotic cells. While the downstream components of this pathway are well understood, the upstream triggers remain less explored. In this study, we conducted an extensive analysis of inhibitors targeting various mitochondrial electron transport chain (ETC) complexes to investigate their potential as activators of the PINK1-Parkin pathway. We identified cloflucarban, an antibacterial compound, as a novel pathway activator that simultaneously inhibits mitochondrial complexes III and V, and V. RNA interference (RNAi) confirmed that the dual inhibition of these complexes activates the PINK1-Parkin pathway. Intriguingly, we discovered that albumin, specifically bovine serum albumin (BSA) and human serum albumin (HSA) commonly present in culture media, can hinder carbonyl cyanide m-chlorophenyl hydrazone (CCCP)-induced pathway activation. However, cloflucarban's efficacy remains unaffected by albumin, highlighting its reliability for studying the PINK1-Parkin pathway. This study provides insights into the activation of the upstream PINK1-Parkin pathway and underscores the influence of culture conditions on research outcomes. Cloflucarban emerges as a promising tool for investigating mitochondrial quality control and neurodegenerative diseases.
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Carbanilidas , Proteínas Quinasas , Ubiquitina-Proteína Ligasas , Humanos , Proteínas Quinasas/metabolismo , Reproducibilidad de los Resultados , Ubiquitina-Proteína Ligasas/metabolismo , Mitocondrias/metabolismo , Albúminas/metabolismoRESUMEN
PURPOSE: The aim of this study was to assess the use of a new medical device to elevate depressed skull fractures (DSFs) in newborns and minor infants. METHODS: Nine patients (ranging from 1 day to 9 months of age) with simple DSF underwent skull elevation by a new elevator medical device. This medical device comprises two elements: a pediatric resuscitator (CPR mask) connected to a 50-ml syringe. Pediatric CPR face mask is placed on the depressed region and negative pressure is generated through syringe plunger elevation until fracture reduction is observed. RESULTS: Fracture reduction was confirmed in eight of nine patients by computed tomography scan without underlying brain damage and associated complications. Skull asymmetry was eliminated recovering normal shape. Up to now, there are no neurological concerns. Another treatment was chosen to be applied for one patient who did not respond to manipulation. CONCLUSION: The new device is a safe, affordable, and effective choice in the treatment of simple depressed skull fractures in newborns and minor infants.
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Descompresión/instrumentación , Fractura Craneal Deprimida/terapia , Diseño de Equipo , Femenino , Humanos , Lactante , Recién Nacido , Masculino , Radiografía , Fractura Craneal Deprimida/diagnóstico por imagen , Resultado del TratamientoRESUMEN
Blue and green ammonia production have been proposed as low-carbon alternatives to emissions-intensive conventional ammonia production. Although much attention has been given to comparing these alternatives, it is still not clear which process has better environmental and economic performance. We present a techno-economic analysis and full life cycle assessment to compare the economics and environmental impacts of blue and green ammonia production. We address the importance of time horizon in climate change impact comparisons by employing the Technology Warming Potential, showing that methane leakage can exacerbate the climate change impacts of blue ammonia in short time horizons. We represent a constrained renewable electricity availability scenario by comparing the climate change impact mitigation efficiency per kWh of renewable electricity. Our work emphasizes the importance of maintaining low natural gas leakage for sustainability of blue ammonia, and the potential for technological advances to further reduce the environmental impacts of photovoltaics-based green ammonia.
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The CO2 -to-aromatics process is a chemical reaction that converts carbon dioxide (CO2 ) into valuable petrochemical, i. e., aromatics (especially, benzene, toluene, and xylene) over the metal/zeolite bifunctional catalytic systems. These aromatics are used in producing plastics, fibers, and other industrial products, which are currently exclusively sourced from fossil-derived feedstocks. The significance of this process lies in its potential to mitigate climate change by reducing greenhouse gas emissions and simultaneously producing valuable chemicals. Consequently, these CO2 -derived aromatics can reduce the reliance on fossil fuels as a source of feedstocks, which can help to promote a more sustainable and circular economy. Owing to the existence of a wider straight channel favoring the aromatization process, zeolite ZSM-5 is extensively used to yield aromatics during CO2 hydrogenation over bifunctional (metal/zeolite) catalytic systems. To provide a better understanding of this unique property of zeolite ZSM-5, this work investigates the impact of particle size and hierarchy of the zeolite and how these govern the reaction performance and the overall selectivity. As a result, an improved understanding of the zeolite-catalyzed hydrocarbon conversion process has been obtained.
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The valorization of CO2 to produce high-value chemicals, such as methanol and hydrocarbons, represents key technology in the future net-zero society. Herein, we report further investigation of a PdZn/ZrO2 + SAPO-34 catalyst for conversion of CO2 and H2 into propane, already presented in a previous work. The focus of this contribution is on the scale up of this catalyst. In particular, we explored the effect of mixing (1:1 mass ratio) and shaping the two catalyst functions into tablets and extrudates using an alumina binder. Their catalytic performance was correlated with structural and spectroscopic characteristics using methods such as FT-IR and X-ray absorption spectroscopy. The two scaled-up bifunctional catalysts demonstrated worse performance than a 1:1 mass physical mixture of the two individual components. Indeed, we demonstrated that the preparation negatively affects the element distribution. The physical mixture is featured by the presence of a PdZn alloy, as demonstrated by our previous work on this sample and high hydrocarbon selectivity among products. For both tablets and extrudates, the characterization showed Zn migration to produce Zn aluminates from the alumina binder phase upon reduction. Moreover, the extrudates showed a remarkable higher amount of Zn aluminates before the activation rather than the tablets. Comparing tablets and extrudates with the physical mixture, no PdZn alloy was observed after activation and only the extrudates showed the presence of metallic Pd. Due to the Zn migration, SAPO-34 poisoning and subsequent deactivation of the catalyst could not be excluded. These findings corroborated the catalytic results: Zn aluminate formation and Pd0 separation could be responsible for the decrease of the catalytic activity of the extrudates, featured by high methane selectivity and unconverted methanol, while tablets displayed reduced methanol conversion to hydrocarbons mainly attributed to the partial deactivation of the SAPO-34.
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Background: Plasma cell neoplasms are characterized by the neoplastic proliferation of a single clone of plasma cells. Solitary plasmacytomas most often occur in bone, but they can also be found in soft tissues. Case Description: A 53-year-old male presented with localized sacral pain and urinary incontinence. His radiographic studies showed a solitary sacral plasmacytoma (i.e., involving the bone). He was successfully managed with high-dose dexamethasone and microwave ablation (MWA). Conclusion: Plasmacytomas of bone can be occasionally successfully managed with MWA, adjuvant cytoreduction therapy, and high doses of dexamethasone.
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The PINK1/Parkin pathway plays an important role in maintaining a healthy pool of mitochondria. Activation of this pathway can lead to apoptosis, mitophagy, or mitochondrial-derived vesicle formation, depending on the nature of mitochondrial damage. The signaling by which PINK/Parkin activation leads to these different mitochondrial outcomes remains understudied. Here we present evidence that cannabidiol (CBD) activates the PINK1-Parkin pathway in a unique manner. CBD stimulates PINK1-dependent Parkin mitochondrial recruitment similarly to other well-studied Parkin activators but with a distinctive shift in the temporal dynamics and mitochondrial fates. The mitochondrial permeability transition pore inhibitor cyclosporine A exclusively diminished the CBD-induced PINK1/Parkin activation and its associated mitochondrial effects. Unexpectedly, CBD treatment also induced elevated production of mitochondrial-derived vesicles (MDV), a potential quality control mechanism that may help repair partial damaged mitochondria. Our results suggest that CBD may engage the PINK1-Parkin pathway to produce MDV and repair mitochondrial lesions via mitochondrial permeability transition pore opening. This work uncovered a novel link between CBD and PINK1/Parkin-dependent MDV production in mitochondrial health regulation.
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Cannabidiol , Mitofagia , Mitocondrias , Proteínas Quinasas , Ubiquitina-Proteína LigasasRESUMEN
Synthetic triterpenoids, 2-cyano-3,12-dioxooleana-1,9-dien-28-oic acid (CDDO) and its derivatives are known to have potent anti-cancer and anti-inflammatory activities. The mechanisms of actions of CDDO and its derivatives as potential therapeutics remain elusive. Previous studies found that CDDO-Me triggers apoptosis by inducing extracellular Ca2+ influx followed by endoplasmic reticulum (ER)-derived vacuolation. Since Ca2+ activity in cells is dynamic and needs to be tracked in real time in living cells, we report a high-throughput and high-content imaging method to track CDDO-induced Ca2+ fluctuation in both ER and cytosol with MATLAB script for data analysis and visualization.
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Antineoplásicos , Ácido Oleanólico , Triterpenos , Antineoplásicos/farmacología , Apoptosis , Ácido Oleanólico/análogos & derivados , Ácido Oleanólico/farmacologíaRESUMEN
In order to empower a circular carbon economy for addressing global CO2 emissions, the production of carbon-neutral fuels is especially desired, since addressing the global fuel demand via this route has the potential to significantly mitigate carbon emissions. In this study, we report a multifunctional catalyst combination consisting of a potassium promoted iron catalyst (Fe-K) and platinum containing zeolite beta (Pt-beta) which produces an almost entirely paraffinic mixture (up to C10 hydrocarbons) via CO2 hydrogenation in one step. Here, the Fe catalyst is responsible for modified Fischer-Tropsch synthesis from CO2 while Pt-beta is instrumental in tuning the product distribution almost entirely towards paraffins (both linear and branched) presumably via a combination of cracking and hydrogenation. The optimal temperature of operation was estimated to be 325 °C for the production of higher paraffins (C5 -C10 ) with a selectivity of ca. 28 % at a CO2 conversion of ca. 31 %.