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1.
Angew Chem Int Ed Engl ; : e202415729, 2024 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-39294096

RESUMEN

For photoelectrocatalytic cells, a limitation exists in finding appropriate photoelectrode configurations that couple efficient extraction of high-energy electrons from absorbed photons and selective catalysis. Here we report an organic p-n junction approach to fabricate molecular photoelectrodes for conversion of solar energy and nitrate into valuable ammonia product. Solar irradiation of the photoelectrode generates charge-separated states with electrons and holes spatially separated at the n-type and p-type components, as revealed by surface photovoltage mapping, at a quantum yield of 90%. The high-flux photogenerated electrons are rapidly transferred to the catalyst for solar ammonia production from nitrate reduction at an external quantum efficiency (EQE) and an internal quantum efficiency (IQE) of 57% and 86%, respectively. Time-resolved spectroscopic studies reveal that the large IQE originates from the combined high efficiencies for photoelectron generation, catalyst activation and dark catalysis. In a flow-cell setup coupled with a silicon solar cell, the photoelectrode without bias generates photocurrent of 57 mA cm-2 and ammonia at an EQE of 52%.

2.
BMC Nurs ; 23(1): 659, 2024 Sep 16.
Artículo en Inglés | MEDLINE | ID: mdl-39285272

RESUMEN

BACKGROUND: Clinical nurses face high-pressure situations requiring rapid decision-making and skilled intervention, impacting their psychological responses and emergency capabilities. Understanding the relationships between psychological factors like gratitude and meaning in life is crucial for improving nurses' performance in emergencies. This study explores the mediating role of gratitude and meaning in life in the impact of psychological responses on clinical nurses' emergency capabilities, aiming to enhance their effectiveness in such situations. METHODS: This study is a multi-center cross-sectional survey. A questionnaire survey was conducted among 1833 clinical nurses in five tertiary hospitals in Anhui Province, China including general information questionnaire, nurses' emergency capability scale, Meaning in life scale, Gratitude scale and Psychological response questionnaire. According to the results of the questionnaire survey, a chain mediating model was constructed and tested. RESULTS: The total score of emergency capability of 1833 clinical nurses was (71.65 ± 10.77), the total score of meaning in life was (50.67 ± 9.04), the total score of gratitude was (30.96 ± 3.57), and the total score of psychological response was 13.00 (6.00, 20.00). The emergency capability of subjects was positively correlated with the meaning in life, the total score of gratitude scale and the scores of each dimension of the two scales, and negatively correlated with the total score of psychological response scale and each dimension of this scale (all P < 0.05). The total effect coefficient, direct effect coefficient and indirect effect coefficient of psychological response on nurses' emergency capability are - 0.230, -0.110 and - 0.120 respectively, that is, the indirect effect accounts for 52.17% of the total effect. Among the indirect effects, the specific mediating effects of gratitude and meaning in life account for 22.50% and 62.50% respectively, and the chain mediating effects of gratitude and meaning in life account for 15.00%. CONCLUSION: Gratitude and meaning in life have multiple mediating roles in the mechanism of psychological response that affecting clinical nurses' emergency capability. Therefore, it is very important to pay attention to dynamically evaluating the psychological response level of clinical nurses, and strive to improve their gratitude and meaning in life, so as to further enhance their emergency response ability.

3.
J Am Chem Soc ; 146(36): 25200-25210, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39222384

RESUMEN

For photoelectrodes to be used in practical catalytic applications, challenges exist in achieving the efficient production and transport of photogenerated charge-separated states. Analogous concepts in traditional inorganic photoelectrodes can be applied to their organic-polymer counterparts with improved charge-separation efficiencies. In this work, we develop photoconductive organic networks to form a high-performance photoelectrode for NO3- reduction to NH3. In the integrated network, interfaces between the organic electron-donating photoconductor and electron-accepting catalyst can generate charge carriers efficiently upon illumination, leading to enhanced charge separation for photoelectrocatalysis. The photoelectrode network is capable of converting NO3- to NH3 at an external quantum efficiency of 13%. By coupling with a BiVO4 photoanode in tandem, the system reduces NO3- to NH3 and oxidizes H2O to O2 simultaneously at Faradaic efficiencies of 95-98% with sustained photocurrents and production yields. Investigation of the photoconductive network by steady-state/time-resolved spectroscopies reveals the efficient generation and transport of free charge carriers in the photoelectrode, providing a basis for high photoelectrocatalytic performances.

4.
Natl Sci Rev ; 11(9): nwae269, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-39188384

RESUMEN

Crystalline matters with periodically arranged atoms found wide applications in modern science and technology. To facilitate the design of new materials and the advancement of existing ones, accurate and efficient models without relying too much on known inputs for predicting the functionalities are essential. Here, we propose an analytical approach for such a purpose, with only the knowledge of the structural chemistry of crystals. Based on the electrostatic interaction between periodically arranged atoms, the 1st, 2nd and 3rd derivatives of interatomic potential, respectively, enable a prediction of ten kinds in total of mechanical, acoustical and thermal properties. Over a thousand measurements are collected from ∼500 literatures, this results in the symmetric mean percentage error (SMPE) within ±25% and the symmetric mean absolute percentage error (SMAPE) ranging from 22%∼74% across all properties predicted, which further enables a revelation of bond characteristics as the most important but implicit origin for functionalities.

5.
J Am Chem Soc ; 2024 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-39192521

RESUMEN

Inspired by the porous structures of photosynthetic organelles, we report here a new type of photoelectrode based on a standalone macroporous conjugated polymer network (MCN) that converts sunlight into high-energy electrons for CO2 reduction to CH3OH. The MCN provides supramolecular cavities with sufficient functional groups that control the structures of photocatalytic assemblies, which circumvents the geometric limitations of traditional inorganic counterparts. Stabilized interfacial contact between MCN and photocatalysts is achieved by strong chemical linkages throughout the network. Solar irradiation of MCN with a cobalt-based catalyst generates highly reducing electrons for the reduction of CO2 to CH3OH at a conversion efficiency of 70%. Production of CH3OH sustains for at least 100 h, with a small decrease in yield rates. Scaling up the photoelectrode from 1 to 100 cm2 results in photocurrent generation stabilized at 0.25 A and continuous CH3OH production at a conversion efficiency of 85%, demonstrating the scalability and high performances.

6.
Phys Chem Chem Phys ; 26(27): 18854-18864, 2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-38946575

RESUMEN

Supported noble metal nanocatalysts typically exhibit strong crystal plane dependent catalytic behavior, but their working mechanism is still unclear. Herein, using anatase TiO2 with well-exposed crystal facets of {101}, {100} and {001} as a prototype support, Pd- and Pt-based supported TiO2 nanocatalysts (TiO2-Pd and TiO2-Pt) were prepared by chemical reduction with NaBH4 as reducer, and they showed a distinct metal-dependent crystal facet effect in the selective hydrogenation of cinamaldehyde (CAL). For Pd-based nanocatalysts, most Pd species on the {100} plane of TiO2 are present in the oxidized form with positive charges and unexpectedly show higher reactivity than the Pd species in the zero-valence state on the {101} and {001} planes. On the contrary, Pt species on all three crystal planes of TiO2 show zero-valence state, with relatively low conversion, but much better selectivity for hydrogenation of a CO bond than Pd-based catalysts. Well-designed experiments manipulating the stability and type of surface oxygen species confirmed that the essence of the crystal facet effect of the catalyst support actually creates a unique nanoconfined interface at the molecular level to construct a surface p-band intermediate state (PBIS), which provides a new alternative channel for surface electron transfer and consequently accelerates the reaction kinetics.

7.
Nat Microbiol ; 9(8): 2144-2159, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38844594

RESUMEN

Nutritional status and pyroptosis are important for host defence against infections. However, the molecular link that integrates nutrient sensing into pyroptosis during microbial infection is unclear. Here, using metabolic profiling, we found that Yersinia pseudotuberculosis infection results in a significant decrease in intracellular glucose levels in macrophages. This leads to activation of the glucose and energy sensor AMPK, which phosphorylates the essential kinase RIPK1 at S321 during caspase-8-mediated pyroptosis. This phosphorylation inhibits RIPK1 activation and thereby restrains pyroptosis. Boosting the AMPK-RIPK1 cascade by glucose deprivation, AMPK agonists, or RIPK1-S321E knockin suppresses pyroptosis, leading to increased susceptibility to Y. pseudotuberculosis infection in mice. Ablation of AMPK in macrophages or glucose supplementation in mice is protective against infection. Thus, we reveal a molecular link between glucose sensing and pyroptosis, and unveil a mechanism by which Y. pseudotuberculosis reduces glucose levels to impact host AMPK activation and limit host pyroptosis to facilitate infection.


Asunto(s)
Proteínas Quinasas Activadas por AMP , Glucosa , Macrófagos , Piroptosis , Proteína Serina-Treonina Quinasas de Interacción con Receptores , Yersinia pseudotuberculosis , Animales , Ratones , Proteínas Quinasas Activadas por AMP/metabolismo , Glucosa/metabolismo , Macrófagos/metabolismo , Macrófagos/microbiología , Yersinia pseudotuberculosis/metabolismo , Yersinia pseudotuberculosis/patogenicidad , Fosforilación , Proteína Serina-Treonina Quinasas de Interacción con Receptores/metabolismo , Proteína Serina-Treonina Quinasas de Interacción con Receptores/genética , Infecciones por Yersinia pseudotuberculosis/microbiología , Infecciones por Yersinia pseudotuberculosis/metabolismo , Ratones Endogámicos C57BL
8.
BMC Musculoskelet Disord ; 25(1): 484, 2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38898448

RESUMEN

BACKGROUND: Spinal fractures in patients with ankylosing spondylitis (AS) mainly present as instability, involving all three columns of the spine, and surgical intervention is often considered necessary. However, in AS patients, the significant alterations in bony structure and anatomy result in a lack of identifiable landmarks, which increases the difficulty of pedicle screw implantation. Therefore, we present the clinical outcomes of robotic-assisted percutaneous fixation for thoracolumbar fractures in patients with AS. METHODS: A retrospective review was conducted on a series of 12 patients diagnosed with AS. All patients sustained thoracolumbar fractures between October 2018 and October 2022 and underwent posterior robotic-assisted percutaneous fixation procedures. Outcomes of interest included operative time, intra-operative blood loss, complications, duration of hospital stay and fracture union. The clinical outcomes were assessed using the visual analogue scale (VAS) and Oswestry Disability Index (ODI). To investigate the achieved operative correction, pre- and postoperative radiographs in the lateral plane were analyzed by measuring the Cobb angle. RESULTS: The 12 patients had a mean age of 62.8 ± 13.0 years and a mean follow-up duration of 32.7 ± 18.9 months. Mean hospital stay duration was 15 ± 8.0 days. The mean operative time was 119.6 ± 32.2 min, and the median blood loss was 50 (50, 250) ml. The VAS value improved from 6.8 ± 0.9 preoperatively to 1.3 ± 1.0 at the final follow-up (P < 0.05). The ODI value improved from 83.6 ± 6.1% preoperatively to 11.8 ± 6.6% at the latest follow-up (P < 0.05). The average Cobb angle changed from 15.2 ± 11.0 pre-operatively to 8.3 ± 7.1 at final follow-up (P < 0.05). Bone healing was consistently achieved, with an average healing time of 6 (5.3, 7.0) months. Of the 108 screws implanted, 2 (1.9%) were improperly positioned. One patient experienced delayed nerve injury after the operation, but the nerve function returned to normal upon discharge. CONCLUSION: Posterior robotic-assisted percutaneous internal fixation can be used as an ideal surgical treatment for thoracolumbar fractures in AS patients. However, while robot-assisted pedicle screw placement can enhance the accuracy of pedicle screw insertion, it should not be relied upon solely.


Asunto(s)
Fijación Interna de Fracturas , Vértebras Lumbares , Procedimientos Quirúrgicos Robotizados , Fracturas de la Columna Vertebral , Espondilitis Anquilosante , Vértebras Torácicas , Humanos , Fracturas de la Columna Vertebral/cirugía , Fracturas de la Columna Vertebral/diagnóstico por imagen , Fracturas de la Columna Vertebral/etiología , Masculino , Persona de Mediana Edad , Vértebras Torácicas/cirugía , Vértebras Torácicas/lesiones , Vértebras Torácicas/diagnóstico por imagen , Femenino , Estudios Retrospectivos , Espondilitis Anquilosante/cirugía , Espondilitis Anquilosante/complicaciones , Vértebras Lumbares/cirugía , Vértebras Lumbares/lesiones , Vértebras Lumbares/diagnóstico por imagen , Procedimientos Quirúrgicos Robotizados/métodos , Fijación Interna de Fracturas/métodos , Fijación Interna de Fracturas/instrumentación , Resultado del Tratamiento , Anciano , Tempo Operativo , Tiempo de Internación , Tornillos Pediculares , Adulto , Pérdida de Sangre Quirúrgica/estadística & datos numéricos , Estudios de Seguimiento
9.
Angew Chem Int Ed Engl ; 63(28): e202405746, 2024 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-38666518

RESUMEN

Developing stable electrocatalysts with accessible isolated sites is desirable but highly challenging due to metal agglomeration and low surface stability of host materials. Here we report a general approach for synthesis of single-site Fe electrocatalysts by integrating a solvated Fe complex in conductive macroporous organic networks through redox-active coordination linkages. Electrochemical activation of the electrode exposes high-density coordinately unsaturated Fe sites for efficient adsorption and conversion of reaction substrates such as NO3 - and H2O. Using the electrode with isolated active Fe sites, electrocatalytic NO3 - reduction and H2O oxidation can be coupled in a single cell to produce NH3 and O2 at Faradaic efficiencies of 97 % and 100 %, respectively. The electrode exhibits excellent robustness in electrocatalysis for 200 hours with small decrease in catalytic efficiencies. Both the maximized Fe-site efficiency and the microscopic localization effect of the conductive organic matrix contribute to the high catalytic performances, which provides new understandings in tuning the efficiencies of metal catalysts for high-performance electrocatalytic cells.

10.
Adv Sci (Weinh) ; 11(23): e2401878, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38582515

RESUMEN

In the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron-hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high-performance photocathode for multi-electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high-throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly-functionalized covalent networks for boosting eight-electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo-accumulating assembly and multi-electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems.

11.
Nat Cell Biol ; 26(4): 567-580, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38538837

RESUMEN

Defects in the prelamin A processing enzyme caused by loss-of-function mutations in the ZMPSTE24 gene are responsible for a spectrum of progeroid disorders characterized by the accumulation of farnesylated prelamin A. Here we report that defective prelamin A processing triggers nuclear RIPK1-dependent signalling that leads to necroptosis and inflammation. We show that accumulated prelamin A recruits RIPK1 to the nucleus to facilitate its activation upon tumour necrosis factor stimulation in ZMPSTE24-deficient cells. Kinase-activated RIPK1 then promotes RIPK3-mediated MLKL activation in the nucleus, leading to nuclear envelope disruption and necroptosis. This signalling relies on prelamin A farnesylation, which anchors prelamin A to nuclear envelope to serve as a nucleation platform for necroptosis. Genetic inactivation of necroptosis ameliorates the progeroid phenotypes in Zmpste24-/- mice. Our findings identify an unconventional nuclear necroptosis pathway resulting from ZMPSTE24 deficiency with pathogenic consequences in progeroid disorder and suggest RIPK1 as a feasible target for prelamin A-associated progeroid disorders.


Asunto(s)
Lamina Tipo A , Necroptosis , Animales , Ratones , Lamina Tipo A/genética , Lamina Tipo A/metabolismo , Mutación , Proteína Serina-Treonina Quinasas de Interacción con Receptores/metabolismo , Factor de Necrosis Tumoral alfa/metabolismo
12.
Mol Cell ; 84(5): 938-954.e8, 2024 Mar 07.
Artículo en Inglés | MEDLINE | ID: mdl-38272024

RESUMEN

Phase separation is a vital mechanism that mediates the formation of biomolecular condensates and their functions. Necroptosis is a lytic form of programmed cell death mediated by RIPK1, RIPK3, and MLKL downstream of TNFR1 and has been implicated in mediating many human diseases. However, whether necroptosis is regulated by phase separation is not yet known. Here, we show that upon the induction of necroptosis and recruitment by the adaptor protein TAX1BP1, PARP5A and its binding partner RNF146 form liquid-like condensates by multivalent interactions to perform poly ADP-ribosylation (PARylation) and PARylation-dependent ubiquitination (PARdU) of activated RIPK1 in mouse embryonic fibroblasts. We show that PARdU predominantly occurs on the K376 residue of mouse RIPK1, which promotes proteasomal degradation of kinase-activated RIPK1 to restrain necroptosis. Our data demonstrate that PARdU on K376 of mouse RIPK1 provides an alternative cell death checkpoint mediated by phase separation-dependent control of necroptosis by PARP5A and RNF146.


Asunto(s)
Necroptosis , Separación de Fases , Animales , Ratones , Apoptosis/fisiología , Muerte Celular , Fibroblastos/metabolismo , Necroptosis/genética , Proteína Serina-Treonina Quinasas de Interacción con Receptores/genética , Proteína Serina-Treonina Quinasas de Interacción con Receptores/metabolismo , Ubiquitina-Proteína Ligasas/genética , Ubiquitina-Proteína Ligasas/metabolismo
13.
Nat Struct Mol Biol ; 31(2): 232-245, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38177673

RESUMEN

Autophagy is a lysosome-dependent degradation pathway essential for cellular homeostasis, which decreases with age. However, it is unclear how aging induces autophagy decline. Here we show the role of protein S-palmitoylation in autophagy. We identify the palmitoyl acyltransferase DHHC5 as a regulator of autophagy by mediating the palmitoylation of beclin 1, which in turn promotes the formation of ATG14L-containing class III phosphatidylinositol-3-kinase complex I and its lipid kinase activity by promoting the hydrophobic interactions between beclin 1 and adapter proteins ATG14L and VPS15. In aging brains of human and nonhuman primate, the levels of DHHC5 exhibit a marked decrease in expression. We show that DHHC5 deficiency in neurons leads to reduced cellular protein homeostasis in two established murine models of Alzheimer's disease, which exaggerates neurodegeneration in an autophagy-dependent manner. These findings identify reduction of DHHC5-mediated beclin 1 S-palmitoylation as an underlying mechanism by which aging induces autophagy decline.


Asunto(s)
Aciltransferasas , Proteínas Reguladoras de la Apoptosis , Autofagia , Beclina-1 , Lipoilación , Animales , Humanos , Ratones , Aciltransferasas/metabolismo , Proteínas Reguladoras de la Apoptosis/metabolismo , Beclina-1/genética , Beclina-1/metabolismo , Proteínas de la Membrana/metabolismo , Fosforilación
14.
World J Microbiol Biotechnol ; 40(1): 21, 2023 Nov 24.
Artículo en Inglés | MEDLINE | ID: mdl-37996766

RESUMEN

Cr(VI) is a hazardous environmental pollutant that poses significant risks to ecosystems and human health. We successfully isolated a novel strain of Bacillus mobilis, strain CR3, from Cr(VI)-contaminated soil. Strain CR3 showed 86.70% removal capacity at 200 mg/L Cr(VI), and a good Cr(VI) removal capacity at different pH, temperature, coexisting ions, and electron donor conditions. Different concentrations of Cr(VI) affected the activity of CR3 cells and the removal rate of Cr(VI), and approximately 3.46% of total Cr was immobilized at the end of the reaction. The combination of SEM-EDS and TEM-EDS analysis showed that Cr accumulated both on the cell surface and inside the cells after treatment with Cr(VI). XPS analysis showed that both Cr(III) and Cr(VI) were present on the cell surface, and FTIR results indicated that the presence of Cr on the cell surface was mainly related to functional groups, such as O-H, phosphate, and -COOH. The removal of Cr(VI) was mainly achieved through bioreduction, which primarily occurred outside the cell. Metabolomics analysis revealed the upregulation of five metabolites, including phenol and L-carnosine, was closely associated with Cr(VI) reduction, heavy metal chelation, and detoxification mechanisms. In addition, numerous metabolites were linked to cellular homeostasis exhibited differential expression. Cr(VI) exerted inhibitory effects on the division rate and influenced critical pathways, including energy metabolism, nucleotide metabolism, and amino acid synthesis and catabolism. These findings reveal the molecular mechanism of Cr(VI) removal by strain CR3 and provide valuable insights to guide the remediation of Cr(VI)-contaminated sites.


Asunto(s)
Bacillus , Ecosistema , Humanos , Bacillus/genética , Bacillus/metabolismo , Cromo/toxicidad , Cromo/metabolismo , Biodegradación Ambiental
15.
Environ Sci Pollut Res Int ; 30(48): 106571-106584, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37730979

RESUMEN

In this study, nano-scale hydroxyapatite (HAP) powder was successfully synthesized from waste eggshells and combined with Lysinibacillus cavernae CR-2 to form bio-microcapsules, which facilitated the enhanced removal of Cr(VI) from wastewater. The effects of various parameters, such as bio-microcapsule dosage, HAP dosage, and initial Cr(VI) concentration on Cr(VI) removal, were investigated. Under different treatment conditions, the Cr(VI) removal followed the order of LC@HAP (90.95%) > LC (78.15%) > Free-LC (75.61%) > HAP (6.56%) > NM (0.23%) at the Cr(VI) initial concentration of 50 mg L-1. Relative to other reaction systems, the LC@HAP treatment exhibited a considerable decrease in total Cr content in the solution, with removal rates surpassing 70%. Additionally, the bio-microcapsules maintained significant biological activity after reacting with Cr(VI). Further characterization using SEM, FTIR, XPS, and XRD revealed that the Cr(VI) removal mechanisms by bio-microcapsules primarily involved biological reduction and HAP adsorption. The adsorption of Cr(III) by HAP predominantly occurred through electrostatic interactions and surface complexation, accompanied by an ion exchange process between Cr(III) and Ca(II). Hence, bio-microcapsules, created by combining L. cavernae with HAP, represent a promising emerging material for the enhanced removal of Cr(VI) pollutants from wastewater.


Asunto(s)
Durapatita , Contaminantes Químicos del Agua , Aguas Residuales , Cápsulas , Contaminantes Químicos del Agua/análisis , Cromo/análisis , Adsorción , Concentración de Iones de Hidrógeno , Cinética
16.
Proc Natl Acad Sci U S A ; 120(39): e2308079120, 2023 09 26.
Artículo en Inglés | MEDLINE | ID: mdl-37733743

RESUMEN

TAK1 is a key modulator of both NF-κB signaling and RIPK1. In TNF signaling pathway, activation of TAK1 directly mediates the phosphorylation of IKK complex and RIPK1. In a search for small molecule activators of RIPK1-mediated necroptosis, we found R406/R788, two small molecule analogs that could promote sustained activation of TAK1. Treatment with R406 sensitized cells to TNF-mediated necroptosis and RIPK1-dependent apoptosis by promoting sustained RIPK1 activation. Using click chemistry and multiple biochemical binding assays, we showed that treatment with R406 promotes the activation of TAK1 by directly binding to TAK1, independent of its original target Syk kinase. Treatment with R406 promoted the ubiquitination of TAK1 and the interaction of activated TAK1 with ubiquitinated RIPK1. Finally, we showed that R406/R788 could promote the cancer-killing activities of TRAIL in vitro and in mouse models. Our studies demonstrate the possibility of developing small molecule TAK1 activators to potentiate the effect of TRAIL as anticancer therapies.


Asunto(s)
Apoptosis , Neoplasias , Animales , Ratones , Muerte Celular , Citosol , Neoplasias/tratamiento farmacológico , Neoplasias/genética , Ubiquitinación
17.
J Am Chem Soc ; 145(39): 21491-21501, 2023 Oct 04.
Artículo en Inglés | MEDLINE | ID: mdl-37733833

RESUMEN

Electrochemical nitrate (NO3-) reduction in aqueous media provides a useful approach for ammonia (NH3) synthesis. While efforts are focused on developing catalysts, the local microenvironment surrounding the catalyst centers is of great importance for controlling electrocatalytic performance. Here, we demonstrate that a self-assembled molecular iron catalyst integrated in a free-standing conductive hydrogel is capable of selective production of NH3 from NO3- at efficiencies approaching unity. With the electrocatalytic hydrogel, the NH3 selectivity is consistently high under a range of negative biases, which results from the hydrophobicity increase of the polycarbazole-based electrode substrate. In mildly acidic media, proton reduction is suppressed by electro-dewetting of the hydrogel electrode, enhancing the selectivity of NO3- reduction. The electrocatalytic hydrogel is capable of continuous production of NH3 for at least 100 h with NH3 selectivity of ∼89 to 98% at high current densities. Our results highlight the role of constructing an internal hydrophobic surface for electrocatalysts in controlling selectivity in aqueous media.

18.
Water Environ Res ; 95(9): e10924, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37650371

RESUMEN

This study investigates the biomineralization of lead ions by Aspergillus niger from aqueous environments, focusing on the dynamic effects of fungal metabolism and biological components. Three biomolecules (glutamate, methionine, and lysine) were used to induce lead oxalate mineralization under lead stress. Comparative experiments were conducted to analyze the growth characteristics and Pb (II) removal ability of A. niger, as well as the morphological and structural properties of the resulting lead oxalate minerals using inductively coupled plasma atomic emission spectroscopy, X-ray powder diffraction, and scanning electron microscopy-energy dispersive spectroscopy techniques. The findings reveal that A. niger plays a crucial role in controlling the mineralization process of Pb (II), with biomineralization experiments demonstrating the specific morphogenesis of lead oxalate over time. Additionally, the inclusion of the three biomolecules in the system indirectly influenced the rate of Pb (II) removal and mineral morphology. These results contribute to a better understanding of A. niger-mediated biomineralization process of lead oxalate and suggest its potential application in the removal of Pb (II) from aqueous environments, particularly in combination with amino acids for enhanced immobilization and mineral recovery. PRACTITIONER POINTS: Fungal activity and amino acids play a crucial role in shaping lead oxalate crystals during water treatment processes. Specific amino acids can effectively delay lead oxalate recrystallization, enhancing the stability and removal efficiency of the crystals. Biomineralization mediated by fungi offers a promising and eco-friendly approach for lead removal and recovery in wastewater treatment. Exploring the influence of organic additives and fungal metabolism on crystal growth provides valuable insights for developing efficient remediation strategies. Further research on the utilization of fungi and amino acids can help with innovative and sustainable wastewater treatment technologies.


Asunto(s)
Aminoácidos , Aspergillus niger , Plomo , Biomineralización , Iones
19.
Nat Commun ; 14(1): 4066, 2023 07 10.
Artículo en Inglés | MEDLINE | ID: mdl-37429863

RESUMEN

Despite advances in cancer treatment, immune checkpoint blockade (ICB) only achieves complete response in some patients, illustrating the need to identify resistance mechanisms. Using an ICB-insensitive tumor model, here we discover cisplatin enhances the anti-tumor effect of PD-L1 blockade and upregulates the expression of Ariadne RBR E3 ubiquitin-protein ligase 1 (ARIH1) in tumors. Arih1 overexpression promotes cytotoxic T cell infiltration, inhibits tumor growth, and potentiates PD-L1 blockade. ARIH1 mediates ubiquitination and degradation of DNA-PKcs to trigger activation of the STING pathway, which is blocked by the phospho-mimetic mutant T68E/S213D of cGAS protein. Using a high-throughput drug screen, we further identify that ACY738, less cytotoxic than cisplatin, effectively upregulates ARIH1 and activates STING signaling, sensitizing tumors to PD-L1 blockade. Our findings delineate a mechanism that tumors mediate ICB resistance through the loss of ARIH1 and ARIH1-DNA-PKcs-STING signaling and indicate that activating ARIH1 is an effective strategy to improve the efficacy of cancer immunotherapy.


Asunto(s)
Antígeno B7-H1 , Neoplasias , Humanos , Antígeno B7-H1/genética , Cisplatino/farmacología , Cisplatino/uso terapéutico , Inhibidores de Puntos de Control Inmunológico/farmacología , Inhibidores de Puntos de Control Inmunológico/uso terapéutico , Neoplasias/tratamiento farmacológico , Linfocitos T , ADN , Ubiquitina-Proteína Ligasas/genética
20.
Environ Sci Technol ; 57(23): 8638-8649, 2023 06 13.
Artículo en Inglés | MEDLINE | ID: mdl-37167064

RESUMEN

Pollutant emissions from coal fires have caused serious concerns in major coal-producing countries. Great efforts have been devoted to suppressing them in China, notably at the notorious Wuda Coalfield in Inner Mongolia. Recent surveys revealed that while fires in this coalfield have been nearly extinguished near the surface, they persist underground. However, the impacts of Hg volatilized from underground coal fires remain unclear. Here, we measured concentrations and isotope compositions of atmospheric Hg in both gaseous and particulate phases at an urban site near the Wuda Coalfield. The atmospheric Hg displayed strong seasonality in terms of both Hg concentrations (5-7-fold higher in fall than in winter) and isotope compositions. Combining characteristic isotope compositions of potential Hg sources and air mass trajectories, we conclude that underground coal fires were still emitting large amounts of Hg into the atmosphere that have been transported to the adjacent urban area in the prevailing downwind direction. The other local anthropogenic Hg emissions were only evident in the urban atmosphere when the arriving air masses did not pass directly through the coalfield. Our study demonstrates that atmospheric Hg isotope measurement is a useful tool for detecting concealed underground coal fires.


Asunto(s)
Contaminantes Atmosféricos , Contaminantes Ambientales , Incendios , Mercurio , Mercurio/análisis , Isótopos de Mercurio/análisis , Carbón Mineral/análisis , China , Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente
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