The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic ...centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect‐rich Bi nanoplates as an efficient noble‐metal‐free N2 reduction electrocatalyst via a low‐temperature plasma bombardment approach. When exclusively using 1H NMR measurements with N2 gas as a quantitative testing method, the defect‐rich Bi(110) nanoplates achieved a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solution at ambient conditions.
Beneficial defects: Defect‐rich bismuth nanoplates achieve a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solutions at ambient conditions because of their poor binding with H adatoms, which increases the selectivity and production rate. Also, 1H NMR measurements with N2 gas ware used as a quantitative test method in aqueous electrolytes.
Two-photon photodynamic therapy (2P-PDT) is a novel minimal invasive cancer treatment method with advantages of deep penetration and intrinsic three-dimensionally localized activation to precisely ...target cancerous tissues. However, the therapeutic efficacy of 2P-PDT is limited by small two-photon absorption cross sections of conventional organic photosensitizers. In addition, traditional photosensitizers generally exhibit weak emission and lack imaging modality. In this work, conjugated polymers and gold nanorods (Au NRs) were integrated to fabricate nano-sized photosensitizers to improve the performance of molecular photosensitizers for 2P-PDT. A molecular photosensitizer, tetraphenylporphyrin, was encapsulated into the conjugated polymer PFV to form conjugated polymer nanoparticles (CPNs), which were then covalently linked to silica coated Au NRs. In these integrated nanoparticles, the two-photon optical properties of tetraphenylporphyrin were first enhanced by fluorescence resonance energy transfer from PFV, then further enhanced by Au NRs through plasmon resonance. A silica shell was utilized as the spacer between Au NRs and CPNs to optimize the enhancement effects. Through the combined enhancement effects of energy transfer and plasmon resonance, two-photon excitation fluorescence and two-photon induced singlet oxygen generation of tetraphenylporphyrin were enhanced by up to 980- and 792-fold, respectively, at a silica spacer thickness of 9 nm. The application of these nanoparticles as photosensitizers for simultaneous two-photon imaging and 2P-PDT treatment have been demonstrated on HeLa cancer cells with high brightness and significantly enhanced cancer cell killing efficiency. These nanoparticles can act as promising nano-photosensitizers for 2P-PDT with simultaneous imaging modality.
Plasmon resonance and energy transfer are integrated to prepare nano-photosensitizers with enhanced two-photon excitation fluorescence and singlet oxygen generation ability.
Major depressive disorder (MDD) is common and disabling, but its neuropathophysiology remains unclear. Most studies of functional brain networks in MDD have had limited statistical power and data ...analysis approaches have varied widely. The REST-meta-MDD Project of resting-state fMRI (R-fMRI) addresses these issues. Twenty-five research groups in China established the REST-meta-MDD Consortium by contributing R-fMRI data from 1,300 patients with MDD and 1,128 normal controls (NCs). Data were preprocessed locally with a standardized protocol before aggregated group analyses. We focused on functional connectivity (FC) within the default mode network (DMN), frequently reported to be increased in MDD. Instead, we found decreased DMN FC when we compared 848 patients with MDD to 794 NCs from 17 sites after data exclusion. We found FC reduction only in recurrent MDD, not in first-episode drug-naïve MDD. Decreased DMN FC was associated with medication usage but not with MDD duration. DMN FC was also positively related to symptom severity but only in recurrent MDD. Exploratory analyses also revealed alterations in FC of visual, sensory-motor, and dorsal attention networks in MDD. We confirmed the key role of DMN in MDD but found reduced rather than increased FC within the DMN. Future studies should test whether decreased DMN FC mediates response to treatment. All R-fMRI indices of data contributed by the REST-meta-MDD consortium are being shared publicly via the R-fMRI Maps Project.
Direct deprotonation represents an extremely simple, straightforward, and atom‐economic strategy to activate pronucleophiles bearing an acidic proton. However, the difficulty often arises in ...activating pronucleophiles with high pKa values by using conventional chiral tertiary amines. To overcome this challenge, a handful of novel chiral Brønsted superbases, including amidines, guanidines, cyclopropenimines, and iminophosphoranes, have been discovered in recent years. This minireview focuses on the application of these organo‐superbases in the catalytic asymmetric reactions of weakly acidic pronucleophiles, and highlights their comparison to the conventional tertiary amines, demonstrating the highly efficient deprotonation processes and stereoselectivity controlled conversions of the superbases. The advantage of these new superbases brings a great opportunity for developing more asymmetric transformations of weakly acidic pronucleophiles.
Superbase: This Minireview focuses on chiral organo‐superbases as catalysts in asymmetric reactions of pronucleophiles with high pKa values. The performance of the organo‐superbases, compared to conventional tertiary amine bases, is highlighted. The advantage of these new superbases lies in the opportunity to develop more asymmetric transformations of weakly acidic pronucleophiles.
Aberrant topological organization of whole-brain networks has been inconsistently reported in studies of patients with major depressive disorder (MDD), reflecting limited sample sizes. To address ...this issue, we utilized a big data sample of MDD patients from the REST-meta-MDD Project, including 821 MDD patients and 765 normal controls (NCs) from 16 sites. Using the Dosenbach 160 node atlas, we examined whole-brain functional networks and extracted topological features (e.g., global and local efficiency, nodal efficiency, and degree) using graph theory-based methods. Linear mixed-effect models were used for group comparisons to control for site variability; robustness of results was confirmed (e.g., multiple topological parameters, different node definitions, and several head motion control strategies were applied). We found decreased global and local efficiency in patients with MDD compared to NCs. At the nodal level, patients with MDD were characterized by decreased nodal degrees in the somatomotor network (SMN), dorsal attention network (DAN) and visual network (VN) and decreased nodal efficiency in the default mode network (DMN), SMN, DAN, and VN. These topological differences were mostly driven by recurrent MDD patients, rather than first-episode drug naive (FEDN) patients with MDD. In this highly powered multisite study, we observed disrupted topological architecture of functional brain networks in MDD, suggesting both locally and globally decreased efficiency in brain networks.
Highlights
Graphene oxide-based hybrid networks were fabricated via introducing multi-amino molecule with triple roles (i.e., cross-linker, fire retardant and reducing agent).
The optimized hybrid ...network with mechanically robust, exceptional intumescent effect and ultra-sensitive fire alarm response (~ 0.6 s) can be used as desirable smart fire alarm sensor materials.
Exceptional fire shielding performances, e.g., ~ 60% reduction in peak heat release rate and limiting oxygen index of ~ 36.5%, are achieved, when coated such hybrid network onto combustible polymer foam.
Smart fire alarm sensor (FAS) materials with mechanically robust, excellent flame retardancy as well as ultra-sensitive temperature-responsive capability are highly attractive platforms for fire safety application. However, most reported FAS materials can hardly provide sensitive, continuous and reliable alarm signal output due to their undesirable temperature-responsive, flame-resistant and mechanical performances. To overcome these hurdles, herein, we utilize the multi-amino molecule, named HCPA, that can serve as triple-roles including cross-linker, fire retardant and reducing agent for decorating graphene oxide (GO) sheets and obtaining the GO/HCPA hybrid networks. Benefiting from the formation of multi-interactions in hybrid network, the optimized GO/HCPA network exhibits significant increment in mechanical strength, e.g., tensile strength and toughness increase of ~ 2.3 and ~ 5.7 times, respectively, compared to the control one. More importantly, based on P and N doping and promoting thermal reduction effect on GO network, the excellent flame retardancy (withstanding ~ 1200 °C flame attack), ultra-fast fire alarm response time (~ 0.6 s) and ultra-long alarming period (> 600 s) are obtained, representing the best comprehensive performance of GO-based FAS counterparts. Furthermore, based on GO/HCPA network, the fireproof coating is constructed and applied in polymer foam and exhibited exceptional fire shielding performance. This work provides a new idea for designing and fabricating desirable FAS materials and fireproof coatings.
In the past few years, substantial progress has been made in perovskite light-emitting devices. Both pure green and infrared thin-film perovskite light-emitting devices with external quantum ...efficiency over 20% have been successfully achieved. However, pure-red and blue thin-film perovskite light-emitting diodes still suffer from inferior efficiency. Therefore, the development of efficient and stable thin-film perovskite light-emitting diodes with pure-red and blue emissions is urgently needed for possible applications as a new display technology and solid-state lighting. Here, we demonstrate an efficient light-emitting diode with pure-red emission based on polymer-assisted in situ growth of high-quality all-inorganic CsPbBr0.6I2.4 perovskite nanocrystal films with homogenous distribution of nanocrystals with size 20–30 nm. With this method, we can dramatically reduce the formation temperature of CsPbBr0.6I2.4 and stabilize its perovskite phase. Eventually, we successfully demonstrate a pure-red-emission perovskite light-emitting diode with a high external quantum efficiency of 6.55% and luminance of 338 cd/m2. Furthermore, the device obtains an ultralow turn-on voltage of 1.5 V and a half-lifetime of over 0.5 h at a high initial luminance of 300 cd/m2.
The accurate taxonomic concept of the fungal
Chaetomium
species has been a hard work due to morphological similarity. Chemotaxonomy based on secondary metabolites is a powerful tool for taxonomical ...purposes, which could be used as an auxiliary reference to solve the problems encountered in the classification of
Chaetomium
. Among secondary metabolites produced by
Chaetomium
, cytochalasans and azaphilones exhibited a pattern of distribution and frequency of occurrence that establish them as chemotaxonomic markers for the
Chaetomium
species. This review attempted to elucidate the composition of the
Chaetomium
species and its relationship with classical taxonomy by summarizing the pattern of cytochalasans and azaphilones distribution and biosynthesis in the
Chaetomium
species.
Key points
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Secondary metabolites from the genus Chaetomium are summarized.
•
Cytochalasans and azaphilones could be characteristic metabolites of the Chaetomium species.
•
Cytochalasans and azaphilones could be used to analyze for taxonomical purposes.
Graphical abstract
Aberrant modulation of mitochondrial dynamic network, which shifts the balance of fusion and fission towards fission, is involved in brain damage of various neurodegenerative diseases including ...Parkinson's disease, Huntington's disease and Alzheimer's disease. A recent research has shown that the inhibition of mitochondrial fission alleviates early brain injury after experimental subarachnoid hemorrhage, however, the underlying molecular mechanisms have remained to be elucidated. This study was undertaken to characterize the effects of the inhibition of dynamin-related protein-1 (Drp1, a dominator of mitochondrial fission) on blood-brain barrier (BBB) disruption and neuronal apoptosis following SAH and the potential mechanisms. The endovascular perforation model of SAH was performed in adult male Sprague Dawley rats. The results indicated Mdivi-1(a selective Drp1 inhibitor) reversed the morphologic changes of mitochondria and Drp1 translocation, reduced ROS levels, ameliorated the BBB disruption and brain edema remarkably, decreased the expression of MMP-9 and prevented degradation of tight junction proteins—occludin, claudin-5 and ZO-1. Mdivi-1 administration also inhibited the nuclear translocation of nuclear factor-kappa B (NF-κB), leading to decreased expressions of TNF-ɑ, IL-6 and IL-1ß. Moreover, Mdivi-1 treatment attenuated neuronal cell death and improved neurological outcome. To investigate the underlying mechanisms further, we determined that Mdivi-1 reduced p-PERK, p-eIF2α, CHOP, cleaved caspase-3 and Bax expression as well as increased Bcl-2 expression. Rotenone (a selective inhibitor of mitochondrial complexes I) abolished both the anti-BBB disruption and anti-apoptosis effects of Mdivi-1. In conclusion, these data implied that excessive mitochondrial fission might inhibit mitochondrial complex I to become a cause of oxidative stress in SAH, and the inhibition of Drp1 by Mdivi-1 attenuated early brain injury after SAH probably via the suppression of inflammation-related blood–brain barrier disruption and endoplasmic reticulum stress-based apoptosis.
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•SAH could result in mitochondrial morphological changes, Drp1 translocation onto mitochondria and ROS increase.•Mdivi-1 may induce the expression of mitochondrial complex I to reduce SAH-induced oxidative stress.•Mdivi-1 may inhibit oxidative stress-induced NF-κB-dependent BBB disruption to attenuate brain edema in SAH.•Mdivi-1 protects neuron against apoptosis probably through the inhibition of the PERK/ eIF2α/ CHOP pathway.
Immunotherapies targeting programmed cell death protein 1 (PD-1)/PD-1 ligand (PD-L1) axis have been emerging as a promising therapeutic strategy to treat lung cancer. PD-1 is preferentially expressed ...by activated T lymphocytes; but whether/how its expression by tumor-associated macrophages (TAMs) in lung adenocarcinoma remains elusive. Herein, we investigate the frequency of PD-1 expression on TAMs in mouse allografts by flow cytometry analysis and evaluate the spatial distribution and clinicopathological significance of PD-1+ TAMs in 213 cases of human lung adenocarcinoma specimens by immunohistochemical staining. We find the expression of PD-1 by both mouse and human TAMs. Mouse PD-1+ TAMs possess unique transcriptional profile as compared to PD-1- TAMs. Furthermore, PD-1 is preferentially expressed by CD163+ TAMs in the tumor stroma than those in the tumor islets of lung adenocarcinoma. Stromal PD-1+ TAM infiltration is an independent predictor of reduced survival as determined by univariate (P < .001) and multivariate (P = .023) analysis. Moreover, patients with high stromal PD-1+ TAMs but low tumor cell PD-L1 expression have the shortest survival (P = .0001). Our study demonstrates that PD-1+ TAMs have unique gene expression characteristics and PD-1+ TAMs in the tumor stroma is a potential prognostic factor in lung adenocarcinoma, suggesting that a better understanding of PD-1+ TAMs will be beneficial for immunotherapy of lung adenocarcinoma patients.
•The presence of PD-1+ TAMs was confirmed in mouse Lewis transplanted tumor.•Mouse PD-1+ TAMs have unique gene expression characteristics.•PD-1 was preferentially expressed on the stromal CD163+ TAMs in human lung adenocarcinoma.•Stromal PD-1+ TAM infiltration was an independent predictor of reduced survival of lung adenocarcinoma patients.
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