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Development of single-component organic phosphor attracts increasing interest due to its wide applications in optoelectronic technologies. Theoretically, activating efficient intersystem crossing (ISC) via 1(π, π*) to 3(π, π*) transitions, rather than 1(n, π*) â 3(π, π*) transitions, is an alternative access to purely organic phosphors but remains challenging. Herein, we designed and successfully synthesized the sila-8-membered ring fused biaryl benzoskeleton by transition metal catalysis, which served as a new organic phosphor with efficient 1(π, π*) to 3(π, π*) ISC. We first found that such a compound exhibits a record-long phosphorescence lifetime of 6.5 s at low temperature for single-component organic systems. Then, we developed two strategies to tune their decay channels to evolve such nonemissive molecules into bright phosphors with elongated lifetimes at room temperature: 1) Physic-based design, where quantitative analyses of electron-phonon coupling led us to reveal and hinder the major nonradiative channels, thus lighted up room temperature phosphorescence (RTP) with a lifetime of 480 ms at 298 K; 2) chemical geometry-driven molecular engineering, where a geometry-based descriptor ΔΘT1-S0/ΘS0 was developed for rational screening RTP candidates and further improved the RTP lifetime to 794 ms. This study clearly shows the power of interdiscipline among synthetic methodology, physics-based rational design, and computational modeling, which represents a paradigm for the development of an organic emitter.
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Metal-organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M-HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time-resolved terahertz spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through-space hole transport mechanism through the interlayer sheet π-π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu-HHTP MOF is found to be 65.5â S m-1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.
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BACKGROUND: To understand the mechanisms leading to the enhanced chilling tolerance of kiwifruit by low-temperature conditioning (LTC, 12 °C for 3 days), this study investigated the effect of LTC on chilling tolerance and changes in antioxidant enzyme activities and endogenous hormones. RESULTS: LTC significantly alleviated chilling injury in kiwifruit. Fruits treated with LTC maintained lower respiration and ethylene production and higher firmness. Furthermore, this treatment inhibited the accumulation of malondialdehyde, superoxide radicals and hydrogen peroxide and the increase in membrane permeability and increased the activities of superoxide dismutase, catalase, ascorbate peroxidase and peroxidase under chilling stress. The treatment also maintained higher levels of endogenous abscisic acid (ABA), indole-3-acetic acid (IAA) and zeatin riboside (ZR), lower gibberellic acid (GA3) levels and higher ABA/GA3 and ABA/IAA ratios. CONCLUSION: The results suggested that LTC alleviated chilling injury in kiwifruit by improving antioxidant enzyme activities and maintaining higher levels of endogenous ABA, IAA and ZR, lower GA3 levels and higher ABA/GA3 and ABA/IAA ratios.
Assuntos
Actinidia/metabolismo , Adaptação Fisiológica , Antioxidantes/metabolismo , Temperatura Baixa , Frutas/metabolismo , Reguladores de Crescimento de Plantas/metabolismo , Actinidia/enzimologia , Ascorbato Peroxidases/metabolismo , Catalase/metabolismo , Permeabilidade da Membrana Celular , Respiração Celular , Frutas/enzimologia , Dureza , Peróxido de Hidrogênio/metabolismo , Malondialdeído/metabolismo , Superóxido Dismutase/metabolismo , Superóxidos/metabolismoRESUMO
Oxidative stress-associated endothelial damage is the initiation factor of cardiovascular disease, and protein posttranslational modifications play critical roles in this process. Bcl-2-associated athanogene 3 (BAG3) is a molecular chaperone regulator of the BAG family, which interacts with various proteins and influences cell survival by activating multiple pathways. BAG3 undergoes posttranslational modifications; however, research evaluating BAG3 acetylation and its regulatory mechanism is lacking. In addition, the interacting protein and regulatory mechanism of BAG3 in oxidative stress-associated endothelial damage remain unclear. Here, key molecular interactions and protein modifications of BAG3 were identified in oxidative stress-associated endothelial damage. Endothelial-specific BAG3 knockout in the mouse model starkly enhances oxidative stress-associated endothelial damage and vascular remodeling, while BAG3 overexpression in mice significantly relieves this process. Mechanistically, poly(ADP-ribose) polymerase 1 (PARP1), causing oxidative stress, was identified as a novel physiological substrate of BAG3. Indeed, BAG3 binds to PARP1's BRCT domain to promote its ubiquitination (K249 residue) by enhancing the E3 ubiquitin ligase WWP2, which leads to proteasome-induced PARP1 degradation. Furthermore, we surprisingly found that BAG3 represents a new substrate of the acetyltransferase CREB-binding protein (CBP) and the deacetylase Sirtuin 2 (SIRT2) under physiological conditions. CBP/SIRT2 interacted with BAG3 and acetylated/deacetylated BAG3's K431 residue. Finally, deacetylated BAG3 promoted the ubiquitination of PARP1. This work reveals a novel regulatory system, with deacetylation-dependent regulation of BAG3 promoting PARP1 ubiquitination and degradation via enhancing WWP2, which is one possible mechanism to decrease vulnerability of oxidative stress in endothelial cells.
Assuntos
Proteínas Adaptadoras de Transdução de Sinal , Proteínas Reguladoras de Apoptose , Células Endoteliais , Estresse Oxidativo , Poli(ADP-Ribose) Polimerase-1/metabolismo , Acetilação , Proteínas Adaptadoras de Transdução de Sinal/metabolismo , Animais , Proteínas Reguladoras de Apoptose/metabolismo , Células Endoteliais/metabolismo , Camundongos , Ubiquitina-Proteína Ligases/metabolismo , UbiquitinaçãoRESUMO
Heterostructures constructed from graphene and transition metal dichalcogenides (TMDs) have established a new platform for optoelectronic applications. After a large number of studies, one intriguing debate is the existence of the interfacial exciton in graphene/TMDs. Hereby, by combined optical pump-terahertz probe spectroscopy and transient absorption spectroscopy, we report the observation of the interfacial exciton in graphene/MoS2 heterostructure. With the photon energy well below the band gap of monolayer MoS2, the hot electrons of graphene are transferred to MoS2 within 0.5 ps; subsequently, the relaxation of the holes in graphene and electrons in MoS2 shows an identical time scale of 15-18 ps, which manifests the formation and relaxation of the interfacial exciton in the heterostructure following photoexcitation. Moreover, a model of the carrier heating and photogating effect in graphene is proposed to estimate the amount of transferred charge, which agrees well with the experimental results. Our study provides insights into the dynamics of graphene-based heterostructure interfacial non-equilibrium carriers.
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Hydrogen evolution by alternating conjugated copolymers has attracted much attention in recent years. To study alternating copolymers with data-driven strategies, two types of multidimension fragmentation descriptors (MDFD), structure-based MDFD (SMDFD), and electronic property-based MDFD (EPMDFD), have been developed with machine learning (ML) algorithms for the first time. The superiority of SMDFD-based models has been demonstrated by the highly accurate and universal predictions of electronic properties. Moreover, EPMDFD-based, experimental-parameter-free ML models were developed for the prediction of the hydrogen evolution reaction, displaying excellent accuracy (real-test accuracy = 0.91). The combination of explainable ML approaches and first-principles calculations was employed to explore photocatalytic dynamics, revealing the importance of electron delocalization in the excited state. Virtual designing of high-performance candidates can also be achieved. Our work illustrates the huge potential of ML-based material design in the field of polymeric photocatalysts toward high-performance photocatalysis.