RESUMEN
Calcium-oxygen (Ca-O2) batteries can theoretically afford high capacity by the reduction of O2 to calcium oxide compounds (CaOx) at low cost1-5. Yet, a rechargeable Ca-O2 battery that operates at room temperature has not been achieved because the CaOx/O2 chemistry typically involves inert discharge products and few electrolytes can accommodate both a highly reductive Ca metal anode and O2. Here we report a Ca-O2 battery that is rechargeable for 700 cycles at room temperature. Our battery relies on a highly reversible two-electron redox to form chemically reactive calcium peroxide (CaO2) as the discharge product. Using a durable ionic liquid-based electrolyte, this two-electron reaction is enabled by the facilitated Ca plating-stripping in the Ca metal anode at room temperature and improved CaO2/O2 redox in the air cathode. We show the proposed Ca-O2 battery is stable in air and can be made into flexible fibres that are weaved into textile batteries for next-generation wearable systems.
RESUMEN
The development of next-generation electronics requires scaling of channel material thickness down to the two-dimensional limit while maintaining ultralow contact resistance1,2. Transition-metal dichalcogenides can sustain transistor scaling to the end of roadmap, but despite a myriad of efforts, the device performance remains contact-limited3-12. In particular, the contact resistance has not surpassed that of covalently bonded metal-semiconductor junctions owing to the intrinsic van der Waals gap, and the best contact technologies are facing stability issues3,7. Here we push the electrical contact of monolayer molybdenum disulfide close to the quantum limit by hybridization of energy bands with semi-metallic antimony ([Formula: see text]) through strong van der Waals interactions. The contacts exhibit a low contact resistance of 42 ohm micrometres and excellent stability at 125 degrees Celsius. Owing to improved contacts, short-channel molybdenum disulfide transistors show current saturation under one-volt drain bias with an on-state current of 1.23 milliamperes per micrometre, an on/off ratio over 108 and an intrinsic delay of 74 femtoseconds. These performances outperformed equivalent silicon complementary metal-oxide-semiconductor technologies and satisfied the 2028 roadmap target. We further fabricate large-area device arrays and demonstrate low variability in contact resistance, threshold voltage, subthreshold swing, on/off ratio, on-state current and transconductance13. The excellent electrical performance, stability and variability make antimony ([Formula: see text]) a promising contact technology for transition-metal-dichalcogenide-based electronics beyond silicon.
RESUMEN
TRIM32 is often aberrantly expressed in many types of cancers. Kaposi's sarcoma-associated herpesvirus (KSHV) is linked with several human malignancies, including Kaposi's sarcoma and primary effusion lymphomas (PELs). Increasing evidence has demonstrated the crucial role of KSHV lytic replication in viral tumorigenesis. However, the role of TRIM32 in herpesvirus lytic replication remains unclear. Here, we reveal that the expression of TRIM32 is upregulated by KSHV in latency, and reactivation of KSHV lytic replication leads to the inhibition of TRIM32 in PEL cells. Strikingly, RTA, the master regulator of lytic replication, interacts with TRIM32 and dramatically promotes TRIM32 for degradation via the proteasome systems. Inhibition of TRIM32 induces cell apoptosis and in turn inhibits the proliferation and colony formation of KSHV-infected PEL cells and facilitates the reactivation of KSHV lytic replication and virion production. Thus, our data imply that the degradation of TRIM32 is vital for the lytic activation of KSHV and is a potential therapeutic target for KSHV-associated cancers. IMPORTANCE: TRIM32 is associated with many cancers and viral infections; however, the role of TRIM32 in viral oncogenesis remains largely unknown. In this study, we found that the expression of TRIM32 is elevated by Kaposi's sarcoma-associated herpesvirus (KSHV) in latency, and RTA (the master regulator of lytic replication) induces TRIM32 for proteasome degradation upon viral lytic reactivation. This finding provides a potential therapeutic target for KSHV-associated cancers.
Asunto(s)
Herpesvirus Humano 8 , Proteínas Inmediatas-Precoces , Proteolisis , Transactivadores , Factores de Transcripción , Proteínas de Motivos Tripartitos , Ubiquitina-Proteína Ligasas , Activación Viral , Replicación Viral , Humanos , Apoptosis , Línea Celular , Herpesvirus Humano 8/crecimiento & desarrollo , Herpesvirus Humano 8/metabolismo , Herpesvirus Humano 8/patogenicidad , Herpesvirus Humano 8/fisiología , Proteínas Inmediatas-Precoces/metabolismo , Proteínas Inmediatas-Precoces/genética , Linfoma de Efusión Primaria/virología , Linfoma de Efusión Primaria/metabolismo , Complejo de la Endopetidasa Proteasomal/metabolismo , Sarcoma de Kaposi/virología , Sarcoma de Kaposi/metabolismo , Transactivadores/metabolismo , Transactivadores/genética , Factores de Transcripción/metabolismo , Factores de Transcripción/genética , Proteínas de Motivos Tripartitos/metabolismo , Proteínas de Motivos Tripartitos/genética , Ubiquitina-Proteína Ligasas/metabolismo , Ubiquitina-Proteína Ligasas/genética , Latencia del VirusRESUMEN
Root hair growth has been studied to understand the principles underlying the regulation of directional growth. Arabidopsis (Arabidopsis thaliana) [Ca2+]cyt-ASSOCIATED PROTEIN KINASE 1 (CAP1) maintains normal vesicle trafficking and cytoskeleton arrangement during root hair growth in response to ammonium signaling. In the current study, we identified CAP1 SUPPRESSOR 1 (CAPS1) as a genetic suppressor of the cap1-1 mutation. The CAPS1 mutation largely rescued the short root hair phenotype of cap1-1. Loss of CAPS1 function resulted in significantly longer root hairs in cap1-1. MutMap analysis revealed that CAPS1 is identical to NIMA (NEVER IN MITOSIS A)-RELATED KINASE 2 (NEK2). In addition, our studies showed that NEK2 is expressed in root and root hairs. Its distribution was associated with the pattern of microtubule arrangement and partially co-localized with CAP1. Further biochemical studies revealed that CAP1 physically interacts with NEK2 and may enhance its phosphorylation. Our study suggests that NEK2 acts as a potential phosphorylation target of CAP1 in maintaining the stability of root hair microtubules to regulate root hair elongation.
RESUMEN
Flash Joule heating of highly porous graphene oxide (GO) aerogel monoliths to ultrahigh temperatures is exploited as a low carbon footprint technology to engineer functional aerogel materials. Aerogel Joule heating to up to 3000 K is demonstrated for the first time, with fast heating kinetics (â¼300 K·min-1), enabling rapid and energy-efficient flash heating treatments. The wide applicability of ultrahigh-temperature flash Joule heating is exploited in a range of material fabrication challenges. Ultrahigh-temperature Joule heating is used for rapid graphitic annealing of hydrothermal GO aerogels at fast time scales (30-300 s) and substantially reduced energy costs. Flash aerogel heating to ultrahigh temperatures is exploited for the in situ synthesis of ultrafine nanoparticles (Pt, Cu, and MoO2) embedded within the hybrid aerogel structure. The shockwave heating approach enables high through-volume uniformity of the formed nanoparticles, while nanoparticle size can be readily tuned through controlling Joule-heating durations between 1 and 10 s. As such, the ultrahigh-temperature Joule-heating approach introduced here has important implications for a wide variety of applications for graphene-based aerogels, including 3D thermoelectric materials, extreme temperature sensors, and aerogel catalysts in flow (electro)chemistry.
RESUMEN
Ultrahigh-temperature Joule-heating of carbon nanostructures opens up unique opportunities for property enhancements and expanded applications. This study employs rapid electrical Joule-heating at ultrahigh temperatures (up to 3000 K within 60 s) to induce a transformation in nanocarbon aerogels, resulting in highly graphitic structures. These aerogels function as versatile platforms for synthesizing customizable metal oxide nanoparticles while significantly reducing carbon emissions compared to conventional furnace heating methods. The thermal conductivity of the aerogel, characterized by Umklapp scattering, can be precisely adjusted by tuning the heating temperature. Utilizing the aerogel's superhydrophobic properties enables its practical application in filtration systems for efficiently separating toxic halogenated solvents from water. The hierarchically porous aerogel, featuring a high surface area of 607 m2 g-1, ensures the uniform distribution and spacing of embedded metal oxide nanoparticles, offering considerable advantages for catalytic applications. These findings demonstrate exceptional catalytic performance in oxidative desulfurization, achieving a 98.9% conversion of dibenzothiophene in the model fuel. These results are corroborated by theoretical calculations, surpassing many high-performance catalysts. This work highlights the pragmatic and highly efficient use of nanocarbon structures in nanoparticle synthesis under ultrahigh temperatures, with short heating durations. Its broad implications extend to the fields of electrochemistry, energy storage, and high-temperature sensing.
RESUMEN
Diabetic gastroparesis (DGP) is characterized by delayed gastric emptying of solid food. Nitrergic neuron-mediated fundus relaxation and intragastric peristalsis are pivotal for gastric emptying and are impaired in DGP. Transient receptor potential vanilloid 1 (TRPV1) ion channels are expressed in gastrointestinal vagal afferent nerves and have a potential role in relevant gastrointestinal disorders. In this study, mice with high-fat diet (HFD)-induced type 2 diabetes mellitus (T2DM), associated with gastroparesis, were used to determine the role of TRPV1 in DGP. After feeding with HFD, mice exhibited obesity, hyperglycemia, insulin resistance, and delayed gastric emptying. Cholinergic- and nitrergic neuron-mediated neuromuscular contractions and relaxation were impaired. The antral tone of the DGP mice was attenuated. Interestingly, activating or suppressing TRPV1 facilitated or inhibited gastric fundus relaxation in normal mice. These effects were neutralized by using a nitric oxide synthase (NOS) inhibitor. Activation or suppression of TRPV1 also increased or reduced NO release. TRPV1 was specifically localized with neuronal NOS in the gastric fundus. These data suggest that TRPV1 activation facilitates gastric fundus relaxation by regulating neuronal NOS and promoting NO release. However, these effects and mechanisms disappeared in mice with DGP induced by HFD diet. TRPV1 expression was only marginally decreased in the fundus of DGP mice. TRPV1 dysfunction may be a potential mechanism underlying the dysfunction of DGP gastric nitrergic neuromuscular relaxation.
Asunto(s)
Diabetes Mellitus Tipo 2 , Gastroparesia , Ratones , Animales , Gastroparesia/etiología , Gastroparesia/metabolismo , Diabetes Mellitus Tipo 2/complicaciones , Dieta Alta en Grasa/efectos adversos , Obesidad/metabolismo , Vaciamiento Gástrico , Canales Catiónicos TRPV/metabolismoRESUMEN
Primary ciliary dyskinesia (PCD) is a genetic disorder characterized by ciliary structural abnormalities and dysfunction, leading to chronic rhinosinusitis, otitis media with effusion, bronchiectasis, and infertility. Approximately half of Japanese PCD cases are attributed to variants in the dynein regulatory complex subunit 1 (DRC1) gene, predominantly featuring homogeneous deletions of exons 1-4 spanning 27,748 base pairs on chromosome 2. Here, we report 10 new PCD cases (9 families) in addition to 29 previously reported cases (24 families) caused by DRC1 variants. Among these 39 cases, biallelic DRC1 exon 1-4 deletions were detected in 38 (97.4%). These DRC1 deletions exhibited an identical breakpoint in all PCD cases in the Japanese and Korean populations, strongly suggesting a founder effect. In this study, we performed haplotype analysis, using a whole-exome sequencing dataset of 18 Japanese PCD patients harboring large biallelic DRC1 deletions. We estimated that the founder allele likely emerged 115.1 generations ago (95% confidence interval: 33.7-205.1), suggesting an origin of approximately 3050 years ago, coinciding with the transition from the Jomon period to the early Yayoi period in Japan. Considering the formation of the modern Japanese population, the founder with the DRC1 exon 1-4 deletion likely lived on the Korean peninsula, with the allele later transmitted to Japan through migration. This study provides insights into the origin of the DRC1 copy number variant, the most frequent PCD variant in the Japanese and Korean populations, highlighting the importance of understanding population-specific genetic variations in the context of human migration and disease prevalence.
RESUMEN
INTRODUCTION: Recombinant allergens produced by Escherichia coli (E. coli) system play an important role in the component-resolved diagnostics of allergy and vaccine development. However, incorrect folding of recombinant allergens may affect their application. Therefore, it is very important to monitor the correct folding of recombinant allergens. Currently, there is still a lack of a quality control strategy to solve this problem. In this study, a mite allergen, Der f 2, was taken as an example to establish a novel quality control strategy, which was based on chromatography to isolate the allergen, and on enzyme-linked immunosorbent assay to verify the IgE reactivity of the isolated allergen. METHODS: The nucleotide sequence encoding Der f 2 was codon-optimized and cloned into pET-28a (+) plasmid. Best conditions for the expression of Der f 2 in E. coli were sought. The inclusion body of Der f 2 was denatured and purified by nickel affinity chromatography. Refolding processes were compared using glutathione redox system. The fully and partially folded proteins were separated by anion exchange chromatography, and the IgE reactivity of the isolated proteins was verified by indirect enzyme-linked immunosorbent assay. RESULTS: An optimized 387 bp segment of the Der f 2 coding gene was successfully expressed in E. coli. Best induction conditions included preinduction bacterial density with absorbance value at 600 nm was 0.6, 1 mM isopropyl beta-
RESUMEN
BACKGROUND: Sepsis is a recognized global health challenge that places a considerable disease burden on countries. Although there has been some progress in the study of sepsis, the mortality rate of sepsis remains high. The relationship between serum osmolality and the prognosis of patients with sepsis is unclear. METHOD: Patients with sepsis who met the criteria in the Medical Information Mart for Intensive Care IV database were included in the study. Hazard ratios (HRs) and 95% confidence intervals (CIs) were determined using multivariable Cox regression. The relationship between serum osmolality and the 28-day mortality risk in patients with sepsis was investigated using curve fitting, and inflection points were calculated. RESULTS: A total of 13,219 patients with sepsis were enrolled in the study; the mean age was 65.1 years, 56.9 % were male, and the 28-day mortality rate was 18.8 %. After adjusting for covariates, the risk of 28-day mortality was elevated by 99% (HR 1.99, 95%CI 1.74-2.28) in the highest quintile of serum osmolality (Q5 >303.21) and by 59% (HR 1.59, 95%CI 1.39-1.83) in the lowest quintile (Q1 ≤285.80), as compared to the reference quintile (Q3 291.38-296.29). The results of the curve fitting showed a U-shaped relationship between serum osmolality and the risk of 28-day mortality, with an inflection point of 286.9 mmol/L. CONCLUSION: There is a U-shaped relationship between serum osmolality and the 28-day mortality risk in patients with sepsis. Higher or lower serum osmolality is associated with an increased risk of mortality in patients with sepsis. Patients with sepsis have a lower risk of mortality when their osmolality is 285.80-296.29 mmol/L.
RESUMEN
The establishment of the Clean Development Mechanism (CDM) has greatly improved China's carbon emission trading system. However, due to the unbalanced development of CDM in China, the effects and mechanism of CDM on reducing pollution and carbon are still unclear. In order to explore the effects and mechanism of CDM on the synergistic effects of pollution mitigation and carbon reduction, we first set up a theoretical analysis framework. Utilizing panel data from 254 prefecture-level cities across China spanning from 2004 to 2021, we employ a synergy degree model of composite system to evaluate the synergistic effects of pollution mitigation and carbon reduction. By treating CDM as a quasi-natural experimental research subject, we construct a multi-period difference-in-difference model to assess the CDM projects' effects. Our findings indicate a positive association between CDM projects and the synergistic effects of pollution mitigation and carbon reduction. Heterogeneity analysis reveals that CDM projects located in the western region, areas with lower levels of economic development, non-resource cities, non-old industrial bases, and projects with Certified Emission Reductions issued exhibit the most pronounced synergistic effects. Specially, dynamic policy effect analysis shows that only non-resource cities and non-old industrial bases exhibit enhanced policy implementation regarding CDM. Mechanism analysis demonstrates that CDM primarily enhances synergistic effects through improved energy efficiency, technological innovation and energy transition. These findings enrich empirical investigations concerning market-driven emission reduction policy in China, shedding light on pivotal pathways for synergistic control of pollution mitigation and carbon reduction and offering valuable policy insights for comprehensive economic and social green transformation in China.
RESUMEN
Primary ciliary dyskinesia (PCD) is a hereditary disease caused by pathogenic variants in genes associated with motile cilia. Some variants responsible for PCD are reported to be ethnic-specific or geographical-specific. To identify the responsible PCD variants of Japanese PCD patients, we performed next-generation sequencing of a panel of 32 PCD genes or whole-exome sequencing in 26 newly identified Japanese PCD families. We then combined their genetic data with those from 40 Japanese PCD families reported previously, for an overall analysis of 66 unrelated Japanese PCD families. We conducted Genome Aggregation Database and TogoVar database analyses to reveal the PCD genetic spectrum of the Japanese population and compare with other ethnic groups worldwide. We identified 22 unreported variants among the 31 patients in the 26 newly identified PCD families, including 17 deleterious variants estimated to cause lack of transcription or nonsense-mediated mRNA decay and 5 missense mutations. In all 76 PCD patients from the 66 Japanese families, we identified 53 variants on 141 alleles in total. Copy number variation in DRC1 is the most frequent variant in Japanese PCD patients, followed by DNAH5 c.9018C>T. We found 30 variants specific to the Japanese population, of which 22 are novel. Furthermore, 11 responsible variants in the Japanese PCD patients are common in East Asian populations, while some variants are more frequent in other ethnic groups. In conclusion, PCD is genetically heterogeneous between different ethnicities, and Japanese PCD patients have a characteristic genetic spectrum.
Asunto(s)
Trastornos de la Motilidad Ciliar , Variaciones en el Número de Copia de ADN , Pueblos del Este de Asia , Humanos , Trastornos de la Motilidad Ciliar/genética , Trastornos de la Motilidad Ciliar/patología , Variaciones en el Número de Copia de ADN/genética , Genómica , MutaciónRESUMEN
Norovirus (NoV) infection is a leading cause of acute gastroenteritis (AGE) for people of all ages. Here, we reported the molecular epidemiology and genetic diversity of NoVs among hospitalized patients with AGE between 2016 and 2018 in Shandong Province, China. Two thousand sixty-nine AGE patients from sentinel hospitals were enrolled. The stool samples were collected and tested for NoVs by real-time RT-PCR. The RNA-dependent RNA polymerase (RdRp) and capsid gene of 163 strains were amplified and sequenced for genotyping. Phylogenetic analyses and genomic characterization were conducted with the VP1 and RdRp region of the full genome sequences. Four hundred seventy two (21.76%) samples were NoV-positive. The positive rate in 2016 was higher than those of 2017 and 2018. We observed diverse NoV genotypes. GII.2[P16] emerged in January 2017 and became the dominant genotype between May and June 2017. Phylogenetic analyses showed that our GII.2[P16] genomes clustered in the SC1 in VP1 region, while they belonged to the Emerging Gâ ¡.P16 (2015-2017) clade in RdRp region. Our Gâ ¡.4 strains displayed two amino acid mutations, positions R297H and D372N, in epitope A of the VP1 region. Our study highlighted that NoV is an important pathogen of viral AGE in Shandong and, therefore, it is necessary to strengthen its surveillance.
Asunto(s)
Infecciones por Caliciviridae , Gastroenteritis , Norovirus , Humanos , Norovirus/genética , Epidemiología Molecular , Filogenia , Prevalencia , Gastroenteritis/epidemiología , Genotipo , Mutación , China/epidemiología , Infecciones por Caliciviridae/epidemiología , ARN Polimerasa Dependiente del ARN/genética , Heces , Variación GenéticaRESUMEN
Colloidal nanocrystal (NC) assemblies are promising for optoelectronic, photovoltaic, and thermoelectric applications. However, using these materials can be challenging in actual devices because they have a limited range of thermal conductivity and elastic modulus, which results in heat dissipation and mechanical robustness challenges. Here, we report thermal transport and mechanical measurements on single-domain colloidal PbS nanocrystal superlattices (NCSLs) that have long-range order as well as measurements on nanocrystal films (NCFs) that are comparatively disordered. Over an NC diameter range of 3.0-6.1 nm, we observe that NCSLs have thermal conductivities and Young's moduli that are up to â¼3 times higher than those of the corresponding NCFs. We also find that these properties are more sensitive to NC diameter in NCSLs relative to NCFs. Our measurements and computational modeling indicate that stronger ligand-ligand interactions due to enhanced ligand interdigitation and alignment in NCSLs account for the improved thermal transport and mechanical properties.
Asunto(s)
Nanopartículas , Ligandos , Nanopartículas/químicaRESUMEN
BACKGROUND: Facial symmetry severely affects appearance and function. Large numbers of patients seek orthodontic treatment to improve facial symmetry. However, the correlation between hard- and soft-tissue symmetry is still unclear. Our aim was to investigate the hard- and soft-tissue symmetry in subjects with different levels of menton deviation and sagittal skeletal classes with 3D digital analysis and to investigate the relationship between the entire and individual hard- and soft-tissues. METHODS: A total of 270 adults (135 males and 135 females) consisting of 45 subjects of each sex in each sagittal skeletal classification group. All subjects were further classified into relative symmetry (RS), moderate asymmetry (MA) and severe asymmetry (SA) groups based on the degree of menton deviation from the mid-sagittal plane (MSP). The 3D images were segmented into anatomical structures and mirrored across the MSP after establishing a coordinate system. Original and mirrored images were registered by a best-fit algorithm, and the corresponding root mean square (RMS) values and colormap were obtained. The MannâWhitney U test and Spearman correlation were conducted for statistical analysis. RESULTS: The RMS increased with greater deviations with regard to the deviation of the menton in most of anatomical structures. Asymmetry was represented in the same way regardless of sagittal skeletal pattern. The soft-tissue asymmetry had a significant correlation with dentition in the RS group (0.409), while in the SA group, it was related to the ramus (0.526) and corpus (0.417) in males and was related to the ramus in the MA (0.332) and SA (0.359) groups in females. CONCLUSIONS: The mirroring method combining CBCT and 3dMD provides a new approach for symmetry analysis. Asymmetry might not be influenced by sagittal skeletal patterns. Soft-tissue asymmetry might be reduced by improving the dentition in individuals with RS group, while among those with MA or SA, whose menton deviation was larger than 2 mm, orthognathic treatment should be considered.
Asunto(s)
Mentón , Pueblos del Este de Asia , Asimetría Facial , Imagenología Tridimensional , Adulto , Femenino , Humanos , Masculino , Algoritmos , Pueblo Asiatico , Imagenología Tridimensional/métodos , Asimetría Facial/diagnóstico por imagen , Asimetría Facial/terapia , Mentón/diagnóstico por imagen , DenticiónRESUMEN
As one of the standard electrophysiological signals in the human body, the photoplethysmography contains detailed information about the blood microcirculation and has been commonly used in various medical scenarios, where the accurate detection of the pulse waveform and quantification of its morphological characteristics are essential steps. In this paper, a modular pulse wave preprocessing and analysis system is developed based on the principles of design patterns. The system designs each part of the preprocessing and analysis process as independent functional modules to be compatible and reusable. In addition, the detection process of the pulse waveform is improved, and a new waveform detection algorithm composed of screening-checking-deciding is proposed. It is verified that the algorithm has a practical design for each module, high accuracy of waveform recognition and high anti-interference capability. The modular pulse wave preprocessing and analysis software system developed in this paper can meet the individual preprocessing requirements for various pulse wave application studies under different platforms. The proposed novel algorithm with high accuracy also provides a new idea for the pulse wave analysis process.
Asunto(s)
Algoritmos , Análisis de Sistemas , Humanos , Programas Informáticos , Frecuencia Cardíaca , MicrocirculaciónRESUMEN
CO binding energy has been employed as a descriptor in the catalyst design for the electrochemical CO2 reduction reactions (CO2 RR). The reliability of the descriptor has yet been experimentally verified due to the lack of suitable methods to determine CO binding energies. In this work, we determined the standard CO adsorption enthalpies ( Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ ) of undoped and doped oxide-derived Cu (OD-Cu) samples, and for the first time established the correlation of Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ with the Faradaic efficiencies (FE) for C2+ products. A clear volcano shaped dependence of the FE for C2+ products on Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ is observed on OD-Cu catalysts prepared with the same hydrothermal durations, however, the trend becomes less clear when all catalysts investigated are taken into account. The relative abundance of Cu sites active for the CO2 -to-CO conversion and the further reduction of CO is identified as another key descriptor.
RESUMEN
CO binding energy has been widely employed as a descriptor for effective catalysts in the electrochemical CO2 and CO reduction reactions (CO(2) RR), however, it has yet to be determined experimentally at electrochemical interfaces due to the lack of suitable techniques. In this work, we developed a method to determine the standard adsorption enthalpy of CO on Cu surfaces with quantitative surface enhanced infrared absorption spectroscopy. On dendritic Cu at -0.75â V vs. SHE, the standard adsorption enthalpy, entropy and Gibbs free energy were determined to 1.5±0.5â kJ mol-1 , ≈37.9±13.4â J/(mol K), and ≈-9.8±4.0â kJ mol-1 , respectively. Comparison of the standard adsorption enthalpy of oxide-derived Cu and dendritic Cu, as well as their CORR activities, suggests the presence of stronger binding sites on OD Cu, which could favor multicarbon products. The method developed in this work will help establish the correlation between the CO binding energy and the CO(2) RR activity.
RESUMEN
The presence of disordered region or large interacting surface within proteins significantly challenges the development of targeted drugs, commonly known as the "undruggable" issue. Here, we report a heterogeneous peptide-protein assembling strategy to selectively phosphorylate proteins, thereby activating the necroptotic signaling pathway and promoting cell necroptosis. Inspired by the structures of natural necrosomes formed by receptor interacting protein kinases (RIPK) 1 and 3, the kinase-biomimetic peptides are rationally designed by incorporating natural or D -amino acids, or connecting D -amino acids in a retro-inverso (DRI) manner, leading to one RIPK3-biomimetic peptide PR3 and three RIPK1-biomimetic peptides. Individual peptides undergo self-assembly into nanofibrils, whereas mixing RIPK1-biomimetic peptides with PR3 accelerates and enhances assembly of PR3. In particular, RIPK1-biomimetic peptide DRI-PR1 exhibits reliable binding affinity with protein RIPK3, resulting in specific cytotoxicity to colon cancer cells that overexpress RIPK3. Mechanistic studies reveal the increased phosphorylation of RIPK3 induced by RIPK1-biomimetic peptides, elucidating the activation of the necroptotic signaling pathway responsible for cell death without an obvious increase in secretion of inflammatory cytokines. Our findings highlight the potential of peptide-protein hybrid aggregation as a promising approach to address the "undruggable" issue and provide alternative strategies for overcoming cancer resistance in the future.
Asunto(s)
Apoptosis , Péptidos , Apoptosis/fisiología , Muerte Celular , Fosforilación , Péptidos/farmacología , AminoácidosRESUMEN
Constructing the backbones of polymers with metal atoms is an attractive strategy to develop new functional polymeric materials, but it has yet to be studied due to synthetic challenges. Here, metal atoms are interconnected as the backbones of polymers to yield metal-backboned polymers (MBPs). Rational design of multidentate ligands synthesized via an efficient iterative approach leads to the successful construction of a series of nickel-backboned polymers (NBPs) with well-defined lengths and up to 21 nickel atoms, whose structures are systematically confirmed. These NBPs exhibit strong and length-depended absorption with narrow band gaps, offering promising applications in optoelectronic devices and semiconductors. We also demonstrate the high thermal stability and solution processsability of such nickel-backboned polymers. Our results represent a new opportunity to design and synthesize a variety of new metal-backboned polymers for promising applications in the future.