First-row transition metal-based catalysts have been developed for the oxygen evolution reaction (OER) during the past years, however, such catalysts typically operate at overpotentials (η) ...significantly above thermodynamic requirements. Here, we report an iron/nickel terephthalate coordination polymer on nickel form (NiFeCP/NF) as catalyst for OER, in which both coordinated and uncoordinated carboxylates were maintained after electrolysis. NiFeCP/NF exhibits outstanding electro-catalytic OER activity with a low overpotential of 188 mV at 10 mA cm
in 1.0 KOH, with a small Tafel slope and excellent stability. The pH-independent OER activity of NiFeCP/NF on the reversible hydrogen electrode scale suggests that a concerted proton-coupled electron transfer (c-PET) process is the rate-determining step (RDS) during water oxidation. Deuterium kinetic isotope effects, proton inventory studies and atom-proton-transfer measurements indicate that the uncoordinated carboxylates are serving as the proton transfer relays, with a similar function as amino acid residues in photosystem II (PSII), accelerating the proton-transfer rate.
Plant viruses pose serious threats to stable crop yield. The majority of them are transmitted by insects, which cause secondary damage to the plant host from the herbivore-vector's infestation. What ...is worse, a successful plant virus evolves multiple strategies to manipulate host defenses to promote the population of the insect vector and thereby furthers the disease pandemic. Jasmonate (JA) and its derivatives (JAs) are lipid-based phytohormones with similar structures to animal prostaglandins, conferring plant defenses against various biotic and abiotic challenges, especially pathogens and herbivores. For survival, plant viruses and herbivores have evolved strategies to convergently target JA signaling. Here, we review the roles of JA signaling in the tripartite interactions among plant, virus, and insect vectors, with a focus on the molecular and biochemical mechanisms that drive vector-borne plant viral diseases. This knowledge is essential for the further design and development of effective strategies to protect viral damages, thereby increasing crop yield and food security.
Water oxidation is the bottleneck reaction in artificial photosynthesis. Exploring highly active and stable molecular water oxidation catalysts (WOCs) is still a great challenge. In this study, a ...water‐soluble NiII complex bearing a redox non‐innocent tetraamido macrocyclic ligand (TAML) is found to be an efficient electrocatalyst for water oxidation in neutral potassium phosphate buffer. Controlled‐potential electrolysis experiments show that it can sustain at a steady current of approximately 0.2 mA cm−2 for >7 h at 1.75 V versus normal hydrogen electrode (NHE) without the formation of NiOx. Electrochemical and spectroelectrochemical tests show that the redox‐active ligand, as well as HPO42− in the buffer, participate in the catalytic cycle. More importantly, catalytically active intermediate NiIII(TAML2−)−O. is formed via several proton‐coupled electron transfer processes and reacts with H2O with the assistance of base to release molecular oxygen. Thus, the employment of redox non‐innocent ligands is a useful strategy for designing effective molecular WOCs.
Unblocking the bottleneck: Water oxidation is the bottleneck reaction in artificial photosynthesis. A water‐soluble NiII complex bearing a redox non‐innocent tetraamido macrocyclic ligand (TAML) is found to be an efficient electrocatalyst for water oxidation in neutral potassium phosphate buffer, sustaining a steady current of approximately 0.2 mA cm−2 for >7 h at 1.75 V versus the normal hydrogen electrode without the formation of NiOx.
Pandemics of vector-borne human and plant diseases often depend on the behaviors of their arthropod vectors. Arboviruses, including many bunyaviruses, manipulate vector behavior to accelerate their ...own transmission to vertebrates, birds, insects, and plants. However, the molecular mechanism underlying this manipulation remains elusive. Here, we report that the non-structural protein NSs of Tomato spotted wilt orthotospovirus, a prototype of the Tospoviridae family and the Orthotospovirus genus, is a key viral factor that indirectly modifies vector preference and increases vector performance. NSs suppresses the biosynthesis of plant volatile monoterpenes, which serve as repellents of the vector western flower thrips (WFT, Frankliniella occidentalis). NSs directly interacts with MYC2, the jasmonate (JA) signaling master regulator and its two close homologs MYC3 and MYC4, to disable JA-mediated activation of terpene synthase genes. The dysfunction of the MYCs subsequently attenuates host defenses, increases the attraction of thrips, and improves thrips fitness. Moreover, MYC2 associated with NSs of Tomato zonate spot orthotospovirus, another Euro/Asian-type orthotospovirus, suggesting that MYC2 is an evolutionarily conserved target of Orthotospovirus species for suppression of terpene-based resistance to promote vector performance. These findings elucidate the molecular mechanism through which an orthotospovirus indirectly manipulates vector behaviors and therefore facilitates pathogen transmission. Our results provide insights into the molecular mechanisms by which Orthotospovirus NSs counteracts plant immunity for pathogen transmission.
Neuropeptide Y (NPY) is a neurotransmitter or neuromodulator that mainly exists in the nervous system. It plays a neuroprotective role in organisms and widely participates in the regulation of ...various physiological processes
. Studies in both humans and animal models have been revealed that NPY levels are altered in some neurodegenerative and neuroimmune disorders. NPY plays various roles in these diseases, such as exerting a neuroprotective effect, increasing trophic support, decreasing excitotoxicity, regulating calcium homeostasis, and attenuating neuroinflammation. In this review, we will focus on the roles of NPY in the pathological mechanisms of neurodegenerative and neuroimmune diseases, highlighting NPY as a potential therapeutic target in these diseases.
While extant evidence supports the link between mother phubbing (Mphubbing) and harsh mothering, the current understanding of factors that may affect this relationship is limited.
Hierarchical ...regression analyses were conducted to examine the relation between Mphubbing and harsh mothering, as well as to explore whether mothers' irritability and adolescents' gender would moderate this relationship. The participants included 482 middle school students (51.7 % girls) and their mothers from China.
The results revealed a significant positive association between Mphubbing as reported by adolescents and their perception of harsh mothering. However, the predictive power of Mphubbing for harsh mothering varied based on mothers' irritability and adolescents' gender. Specifically, the association between Mphubbing and harsh mothering was perceived more strongly in girls than in boys, but this gender difference was only observed among adolescents whose mothers rated themselves as high in irritability.
The current study offers a preliminary understanding of the association between Mphubbing and harsh mothering through mothers' irritability and adolescents' gender as moderators, which has certain theoretical and practical implications for comprehending harsh mothering in the digital age.
•A moderated model was formulated to reveal the relationship between mother phubbing, mothers’ irritability, adolescents’ gender, and harsh mothering.•The study examines the combined impact of environmental and individual factors on harsh mothering.•The association between Mphubbing and harsh mothering was perceived more strongly in girls than in boys, but this difference was only observed among adolescents whose mothers rated themselves high in irritability.
Acute necrotizing encephalopathy (ANE) is a rare but distinctive type of acute encephalopathy with global distribution. Occurrence of ANE is usually preceded by a virus-associated febrile illness and ...ensued by rapid deterioration. However, the causal relationship between viral infections and ANE and the exact pathogenesis of ANE remain unclear; both environmental and host factors might be involved. Most cases of ANE are sporadic and nonrecurrent, namely, isolated or sporadic ANE; however, few cases are recurrent and with familial episodes. The recurrent and familial forms of ANE were found to be incompletely autosomal-dominant. Further the missense mutations in the gene encoding the nuclear pore protein Ran Binding Protein 2 (RANBP2) were identified. Although the clinical course and the prognosis of ANE are diverse, the hallmark of neuroradiologic manifestation of ANE is multifocal symmetric brain lesions which are demonstrated by computed tomography (CT) or magnetic resonance imaging (MRI). The treatment of ANE is still under investigation. We summarize the up-to-date knowledge on ANE, with emphasis on prompt diagnosis and better treatment of this rare but fatal disease.
Mesoporous LaFeO3 was used as a p-type visible-light-absorbing semiconductor (VLAS) substrate for light-driven H2 generation. The successful modification of LaFeO3 with a molecular dye (P1*) and a ...molecular hydrogen production catalyst (NiP) paved a novel way to construct DS-PEC photocathodes for solar-driven H2 generation by using VLASs.
Primary skin amyloidosis is a chronic skin disease in which amyloid deposits in the normal skin tissues without involving other organs. At present, the causes and mechanisms of morbidity have not ...been fully elucidated. There are few clinical reports of nodular skin amyloidosis, and the domestic reports are mostly limited cases. This study reported a rare case of a 46-year-old woman with primary localized cutaneous nodular amyloidosis (PLCNA). The patient presented with features of lymphatic malformation, a plexiform nodule of small blisters. Histological examination revealed amyloid deposits involving the superficial and deep dermis with a small number of plasma cells. Further examinations did not reveal evidence of systemic involvement, indicating a PLCNA. The presentation as lymphatic malformation lesions illustrates the importance of clinical pathology. Nodular amyloidosis typically manifests as single or multiple yellow-brown nodules or plaques of a few millimeters to several centimeters. The center of the nodule sometimes shows atrophy and relaxation or forms a bullous. It is recommended to perform a pathological examination to confirm the diagnosis to distinguish it from lymphatic malformation.
One and two scandium ions (Sc3+) are bound strongly to nonheme manganese(IV)–oxo complexes, (N4Py)MnIV(O)2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and (Bn-TPEN)MnIV(O)2+ ...(Bn-TPEN = N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), to form MnIV(O)–(Sc3+)1 and MnIV(O)–(Sc3+)2 complexes, respectively. The binding of Sc3+ ions to the MnIV(O) complexes was examined by spectroscopic methods as well as by DFT calculations. The one-electron reduction potentials of the MnIV(O) complexes were markedly shifted to a positive direction by binding of Sc3+ ions. Accordingly, rates of the electron transfer reactions of the MnIV(O) complexes were enhanced as much as 107–fold by binding of two Sc3+ ions. The driving force dependence of electron transfer from various electron donors to the MnIV(O) and MnIV(O)–(Sc3+)2 complexes was examined and analyzed in light of the Marcus theory of electron transfer to determine the reorganization energies of electron transfer. The smaller reorganization energies and much more positive reduction potentials of the MnIV(O)–(Sc3+)2 complexes resulted in remarkable enhancement of the electron-transfer reactivity of the MnIV(O) complexes. Such a dramatic enhancement of the electron-transfer reactivity of the MnIV(O) complexes by binding of Sc3+ ions resulted in the change of mechanism in the sulfoxidation of thioanisoles by MnIV(O) complexes from a direct oxygen atom transfer pathway without metal ion binding to an electron-transfer pathway with binding of Sc3+ ions.
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