Dysregulated prefrontal control over amygdala is engaged in the pathogenesis of psychiatric diseases including depression and anxiety disorders. Here we show that, in a rodent anxiety model induced ...by chronic restraint stress (CRS), the dysregulation occurs in basolateral amygdala projection neurons receiving mono-directional inputs from dorsomedial prefrontal cortex (dmPFC→BLA PNs) rather than those reciprocally connected with dmPFC (dmPFC↔BLA PNs). Specifically, CRS shifts the dmPFC-driven excitatory-inhibitory balance towards excitation in the former, but not latter population. Such specificity is preferential to connections made by dmPFC, caused by enhanced presynaptic glutamate release, and highly correlated with the increased anxiety-like behavior in stressed mice. Importantly, low-frequency optogenetic stimulation of dmPFC afferents in BLA normalizes the enhanced prefrontal glutamate release onto dmPFC→BLA PNs and lastingly attenuates CRS-induced increase of anxiety-like behavior. Our findings thus reveal a target cell-based dysregulation of mPFC-to-amygdala transmission for stress-induced anxiety.
Layered oxides have become the research focus of cathode materials for sodium‐ion batteries (SIBs) due to the low cost, simple synthesis process, and high specific capacity. However, the poor air ...stability, unstable phase structure under high voltage, and slow anionic redox kinetics hinder their commercial application. In recent years, the concept of manipulating orbital hybridization has been proposed to simultaneously regulate the microelectronic structure and modify the surface chemistry environment intrinsically. In this review, the hybridization modes between atoms in 3d/4d transition metal (TM) orbitals and O 2p orbitals near the region of the Fermi energy level (EF) are summarized based on orbital hybridization theory and first‐principles calculations as well as various sophisticated characterizations. Furthermore, the underlying mechanisms are explored from macro‐scale to micro‐scale, including enhancing air stability, modulating high working voltage, and stabilizing anionic redox chemistry. Meanwhile, the origin, formation conditions, and different types of orbital hybridization, as well as its application in layered oxide cathodes are presented, which provide insights into the design and preparation of cathode materials. Ultimately, the main challenges in the development of orbital hybridization and its potential for the production application are also discussed, pointing out the route for high‐performance practical sodium layered oxide cathodes.
Based on orbital hybridization theory, the challenges of layered oxide cathodes in terms of air stability, high voltage, anion redox chemistry, and improving the intrinsic characteristics through interactions between the 3d/4d transition metal and the O 2p atomic orbitals are summarized. This strategy of modulating orbitals hybridization will promote the development of sodium layered oxide cathodes and its commercialization process.
Semiconducting quantum dots (QDs) have recently triggered a huge interest in constructing efficient hydrogen production systems. It is well established that a large fraction of surface atoms of QDs ...need ligands to stabilize and avoid them from aggregating. However, the influence of the surface property of QDs on photocatalysis is rather elusive. Here, the surface regulation of CdSe QDs is investigated by surface sulfide ions (S2−) for photocatalytic hydrogen evolution. Structural and spectroscopic study shows that with gradual addition of S2−, S2− first grows into the lattice and later works as ligands on the surface of CdSe QDs. In‐depth transient spectroscopy reveals that the initial lattice S2− accelerates electron transfer from QDs to cocatalyst, and the following ligand S2− mainly facilitates hole transfer from QDs to the sacrificial agent. As a result, a turnover frequency (TOF) of 7950 h−1 can be achieved by the S2− modified CdSe QDs, fourfold higher than that of original mercaptopropionic acid (MPA) capped CdSe QDs. Clearly, the simple surface S2− modification of QDs greatly increases the photocatalytic efficiency, which provides subtle methods to design new QD material for advanced photocatalysis.
To unravel how surface sulfide ions (S2−)regulate photocatalytic hydrogen evolution of CdSe quantum dots (QDs), the different roles of introduced S2− on QDs are revealed. The results show that S2− at an earlier stage grows into the lattice and accelerates electron transfer, while afterward the S2− works as ligands and promotes hole transfer, and thus greatly improves the photocatalytic hydrogen evolution efficiency.
The visionary idea that RNA adopts nonbiological roles in today's nanomaterial world has been nothing short of phenomenal. These RNA molecules have ample chemical functionality and self‐assemble to ...form distinct nanostructures in response to external stimuli. They may be combined with inorganic materials to produce nanomachines that carry cargo to a target site in a controlled manner and respond dynamically to environmental changes. Comparable to biological cells, programmed RNA nanomachines have the potential to replicate bone healing in vitro. Here, an RNA–biomineral nanomachine is developed, which accomplishes intrafibrillar and extrafibrillar mineralization of collagen scaffolds to mimic bone formation in vitro. Molecular dynamics simulation indicates that noncovalent hydrogen bonding provides the energy source that initiates self‐assembly of these nanomachines. Incorporation of the RNA–biomineral nanomachines into collagen scaffolds in vivo creates an osteoinductive microenvironment within a bone defect that is conducive to rapid biomineralization and osteogenesis. Addition of RNA‐degrading enzymes into RNA–biomineral nanomachines further creates a stop signal that inhibits unwarranted bone formation in tissues. The potential of RNA in building functional nanostructures has been underestimated in the past. The concept of RNA–biomineral nanomachines participating in physiological processes may transform the nanoscopic world of life science.
An RNA–amorphous calcium phosphate nanomachine that induces extrafibrillar and intrafibrillar mineralization of collagen fibrils and regenerates new bone in a dynamic and programmable manner is developed. This multifunctional nanomachinery is comparable to the function of osteoblasts. The RNA–biomineral nanomachines that simulate physiological processes brings new opportunities and challenges to bone tissue engineering.
Photocatalysts based on g-C3N4 by loading cocatalysts or constructing heterojunctions have shown great potential in solar-driven water oxidation. However, the intrinsic drawbacks of g-C3N4, such as ...poor mass diffusion and charge separation efficiency, remain as the bottleneck to achieve highly efficient water oxidation. Here we report a simple protonation method to improve the activity of g-C3N4. Studies using valence band X-ray photoelectron spectra and steady-state and time-resolved spectroscopy reveal that the promotion of catalytic ability originates from the higher thermodynamical driving force and longer-lived charge separation state, which may provide guidance in designing efficient polymeric semiconductor photocatalysts with desirable kinetics for water oxidation.
C-type lectin receptors (CLRs) play critical roles as pattern-recognition receptors (PRRs) for sensing Candida albicans infection, which can be life-threatening for immunocompromised individuals. ...Here we have shown that Dectin-3 (also called CLECSF8, MCL, or Clec4d), a previously uncharacterized CLR, recognized α-mannans on the surfaces of C. albicans hyphae and induced NF-κB activation. Mice with either blockade or genetically deleted Dectin-3 were highly susceptible to C. albicans infection. Dectin-3 constantly formed heterodimers with Dectin-2, a well-characterized CLR, for recognizing C. albicans hyphae. Compared to their respective homodimers, Dectin-3 and Dectin-2 heterodimers bound α-mannans more effectively, leading to potent inflammatory responses against fungal infections. Together, our study demonstrates that Dectin-3 forms a heterodimeric PRR with Dectin-2 for sensing fungal infection and suggests that different CLRs may form different hetero- and homodimers, which provide different sensitivity and diversity for host cells to detect various microbial infections.
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•Dectin-3 is a subunit of a functional PRR that senses Candida albicans infection•Dectin-3-deficient mice are highly susceptible to fungal infection•Dectin-2 and Dectin-3 form a heterodimeric pattern-recognition receptor•Dectin-2 and Dectin-3 heterodimers have a high affinity for PAMP
• Evolutionary transitions from outcrossing to selfing often occur in heterostylous plants. Selfing homostyles originate within distylous populations and frequently evolve to become reproductively ...isolated species. We investigated this process in 10 species of Primula section Obconicolisteri using phylogenomic approaches and inferred how often homostyly originated from distyly and its consequences for population genetic diversity and floral trait evolution.
• We estimated phylogenetic relationships and reconstructed character evolution using the whole plastome comprised of 76 protein-coding genes. To investigate mating patterns and genetic diversity we screened 15 microsatellite loci in 40 populations. We compared floral traits among distylous and homostylous populations to determine how phenotypically differentiated homostyles were from their distylous ancestors.
• Section Obconicolisteri was monophyletic and we estimated multiple independent transitions from distyly to homostyly. High selfing rates characterised homostylous populations and this was associated with reduced genetic diversity. Flower size and pollen production were reduced in homostylous populations, but pollen size was significantly larger in some homostyles than in distylous morphs.
• Repeated transitions to selfing in section Obconicolisteri are likely to have been fostered by the complex montane environments that species occupy. Unsatisfactory pollinator service is likely to have promoted reproductive assurance in homostyles leading to subsequent population divergence through isolation.
The breakdown of heterostyly to homostyly is a classic system for the investigation of evolutionary transitions from outcrossing to selfing. Loss of sexual polymorphism is characterized by changes to ...population morph structure and floral morphology. Here, we used molecular phylogeography to investigate the geographical context for the breakdown process in Primula chungensis, a species with distylous and homostylous populations.
We genotyped plants from 20 populations throughout the entire range in south-west China using the chloroplast intergenic spacer (trnL-trnF), nuclear internal transcribed spacer (ITS) and 10 nuclear microsatellite loci, and determined the genetic relationships among populations and the variation in floral traits associated with homostyle evolution.
The marker data identified two multi-population lineages (Tibet and Sichuan) and one single-population lineage (Yunnan), a pattern consistent with at least two independent origins of homostyly. Evidence from flower and pollen size variation is consistent with the hypothesis that transitions to selfing have arisen by the same genetic mechanism involving recombination and/or mutation at the distyly linkage group. Nevertheless, flowers of homostylous lineages
have followed divergent evolutionary trajectories following their origin, resulting in populations with both approach and reverse herkogamy.
Our study illustrates a rare example of the near-complete replacement of sexual polymorphism by floral monomorphism in a heterostylous species.
Computational electrochemistry, an important branch of electrochemistry, has shown its advantages in studying electrode/electrolyte interfaces, such as the structures of electric double layers. ...However, modeling electrochemical systems is still a challenge, especially in interface electrochemistry, because not only solvation effects and ion distribution in electrolyte solutions should be considered, but also the treatment of the electrode potential and the response of electrolytes to applied potentials. Here, we review the latest development in the field of computational electrochemistry. We first introduce various energy models used in simulating electrolytes and electrodes at multiple scales. Then, to better explain and compare between different methods, we discuss the calculation methods of solution electrochemistry and interface electrochemistry in separate. At last, we introduce the methods to electrify the interfaces in various multiscale models. This review aims to help understand various levels of methods in simulations of different scenarios in electrochemistry, and summarizes a set of schemes covering multiple scales.
This article is categorized under:
Electronic Structure Theory > Combined QM/MM Methods
Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods
Electronic Structure Theory > Density Functional Theory
(a). Schematic representation of electrochemical interfaces. Components alonge the z axis include the electrode, stern layer (inner Helmholtz layer b1 and outer Helmholtz layer b2), diffuse layer and bulk electrolytes. The red curve represents the decay of electrostatic potential from the positively charged electrode surface into electrolyte solution. (b). The spatial scale and the level of EDL description that can be described by various energy models for interfaces.
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