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Herein, an effective tandem catalysis strategy is developed to improve the selectivity of the CO2 RR towards C2 H4 by multiple distinct catalytic sites in local vicinity. An earth-abundant elements-based tandem electrocatalyst PTF(Ni)/Cu is constructed by uniformly dispersing Cu nanoparticles (NPs) on the porphyrinic triazine framework anchored with atomically isolated nickel-nitrogen sites (PTF(Ni)) for the enhanced CO2 RR to produce C2 H4 . The Faradaic efficiency of C2 H4 reaches 57.3 % at -1.1 V versus the reversible hydrogen electrode (RHE), which is about 6 times higher than the non-tandem catalyst PTF/Cu, which produces CH4 as the major carbon product. The operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that the local high concentration of CO generated by PTF(Ni) sites can facilitate the C-C coupling to form C2 H4 on the nearby Cu NP sites. The work offers an effective avenue to design electrocatalysts for the highly selective CO2 RR to produce multicarbon products via a tandem route.

Porous crystalline metal-organic frameworks (MOFs) are one class of promising electrode materials for CO2 electroreduction reaction (CO2RR) by virtue of their large CO2 adsorption capacities and abundant tunable active sites, but their insulating nature usually leads to low current density. Herein, a two-dimensional (2D) Ni-phthalocyanine-based MOF (NiPc-Ni(NH)4) constructed by 2,3,9,10,16,17,23,24-octaaminophthalocyaninato nickel(II) (NiPc-(NH2)8) and nickel(II) ions attained high electrical conductivity due to the high overlap of d-π conjugation orbitals between the nickel node and the Ni-phthalocyanine-substituted o-phenylenediamine. During CO2RR, the NiPc-Ni(NH)4 nanosheets achieved a high CO Faradaic efficiency of 96.4% at −0.7 V and a large CO partial current density of 24.8 mA cm−2 at −1.1 V, which surpassed all the reported two-dimensional MOF electrocatalysts evaluated in an H-cell. The control experiments and density functional theory (DFT) calculations suggested that the Ni-N4 units of the phthalocyanine ring are the catalytic active sites. This work provides a new route to the design of highly efficient porous framework materials for the enhanced electrocatalysis via improving electrical conductivity.

The electrocatalytic conversion of CO2 into value-added chemicals is a promising approach to realize a carbon-energy balance. However, low current density still limits the application of the CO2 electroreduction reaction (CO2 RR). Metal-organic frameworks (MOFs) are one class of promising alternatives for the CO2 RR due to their periodically arranged isolated metal active sites. However, the poor conductivity of traditional MOFs usually results in a low current density in CO2 RR. We have prepared conductive two-dimensional (2D) phthalocyanine-based MOF (NiPc-NiO4 ) nanosheets linked by nickel-catecholate, which can be employed as highly efficient electrocatalysts for the CO2 RR to CO. The obtained NiPc-NiO4 has a good conductivity and exhibited a very high selectivity of 98.4 % toward CO production and a large CO partial current density of 34.5 mA cm-2 , outperforming the reported MOF catalysts. This work highlights the potential of conductive crystalline frameworks in electrocatalysis.

l -Tryptophan (Trp) metabolites and related neurotransmitters play crucial roles in physiological functions, and their imbalances are implicated in the pathology of depression, Alzheimer's disease and other diseases. Measurement of Trp metabolites and related neurotransmitters possesses a great potential to elucidate the disease mechanisms and evaluate the outcomes of therapeutic interventions. A simple, rapid, sensitive and specific liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for simultaneous determination of Trp, l -kynurenine (Kyn), kynurenic acid (Kyna), 3-hydroxykynurenine (3-HK), 5-hydroxytryptamine (5-HT), 5-hydroxyindoleacetic acid (5-HIAA), norepinephrine (NE), l -glutamic acid (Glu), γ-aminobutyric acid (GABA) and acetylcholine (ACh) in mice serum and the brain tissues in a single chromatographic run. Samples were spiked with the internal standard, mixed with trifluoroacetic acid to precipitate protein and analyzed by LC-MS/MS. Chromatographic separation was achieved using a Restek Ultra Aqueous C18 column in combination with a gradient elution within 8 min. Mass spectrometric detection was performed using multiple reaction monitoring with electrospray ionization source in positive mode. The method exhibited good selectivity and correlation coefficient values for the calibration curves of each analyte were >0.99. The limit of detection and quantification ranged from 0.96 to 24.48 nmol/L and 3.42 to 244.82 nmol/L, respectively. The intra- and inter-day precision were ≤13.92%. All analytes were stable in prepared samples at room temperature in the autosampler for 24 h. This method was successfully applied to the analysis of biological samples from control and chronic mild stress (CMS) induced depression mice. It was found that Kyn and 3-HK pathways were enhanced by CMS, while the levels of Trp, Kyna, 5-HIAA, Glu, GABA and ACh were significantly reduced. The changes in 5-HT and NE levels were not uniform in the periphery and the brain. This method can therefore be applied to analyze Trp metabolites and related neurotransmitters levels to monitor disease states, study the mechanisms and outcomes of therapeutic interventions.

Amyloid-β1-42 (Aβ1-42) oligomers play an important role at the early stage of Alzheimer's disease (AD) and have been a vital target in the development of therapeutic drugs for AD. Cajaninstilbene acid (CSA), a major bioactive stilbene isolated from pigeon pea (Cajanus cajan) leaves, exerted the neuroprotective property in our previous studies. The present study utilized a validated mouse model of early-stage AD induced by bilateral injection of Aβ1-42 oligomers into hippocampal CA1 regions (100 pmol/mouse) to investigate the cognitive enhancing effects of CSA and the underlying mechanism, by a combination of animal behavioral tests, immunohistochemistry, liquid chromatography-tandem mass spectrometry analysis, and Western blot methods. Intragastric administration of CSA (7.5, 15, and 30 mg/kg) attenuated the impairment of learning and memory induced by Aβ1-42 oligomers. CSA stimulated Aβ clearance and prevented microglial activation and astrocyte reactivity in the hippocampus of model mice. It also decreased the high levels of Glu but increased the low levels of GABA. In addition, CSA inhibited excessive expression of GluN2B-containing NMDARs and upregulated the downstream PKA/CREB/BDNF/TrkB signaling pathway. These results suggest that CSA could be a potential therapeutic agent at the early stage of AD.

Metal-organic frameworks (MOFs) are promising alternative precursors for the fabrication of heteroatom-doped carbon materials for energy storage and conversion. However, the direct pyrolysis of bulk MOFs usually gives microporous carbonaceous materials, which significantly hinder the mass transportation and the accessibility of active sites. Herein, N-doped carbon aerogels with hierarchical micro-, meso-, and macropores were fabricated through one-step pyrolysis of zeolitic imidazolate framework-8/carboxymethylcellulose composite gel. Owing to the hierarchical porosity, high specific surface area, favorable conductivity, excellent thermal and chemical stability, the as-prepared N-doped carbon aerogel exhibits excellent oxygen reduction reaction (ORR) activity, long-term durability, and good methanol tolerance in alkaline medium. This work thus provides a new way to fabricate new types of MOF-derived carbon aerogels for various applications.

The electroreduction of CO2 to value-added chemicals such as CO is a promising approach to realize carbon-neutral energy cycle, but still remains big challenge including low current density. Covalent organic frameworks (COFs) with abundant accessible active single-sites can offer a bridge between homogeneous and heterogeneous electrocatalysis, but the low electrical conductivity limits their application for CO2 electroreduction reaction (CO2 RR). Here, a 2D conductive Ni-phthalocyanine-based COF, named NiPc-COF, is synthesized by condensation of 2,3,9,10,16,17,23,24-octa-aminophthalocyaninato Ni(II) and tert-butylpyrene-tetraone for highly efficient CO2 RR. Due to its highly intrinsic conductivity and accessible active sites, the robust conductive 2D NiPc-COF nanosheets exhibit very high CO selectivity (>93%) in a wide range of the applied potentials of -0.6 to -1.1 V versus the reversible hydrogen electrode (RHE) and large partial current density of 35 mA cm-2 at -1.1 V versus RHE in aqueous solution that surpasses all the conventional COF electrocatalysts. The robust NiPc-COF that is bridged by covalent pyrazine linkage can maintain its CO2 RR activity for 10 h. This work presents the implementation of the conductive COF nanosheets for CO2 RR and provides a strategy to enhance energy conversion efficiency in electrocatalysis.

Cajaninstilbene acid (CSA), a bioactive constituent isolated from pigeon pea leaves, exhibited neuroprotective activities in previous studies. The present study aims to evaluate the antidepressant effects of CSA by using behavioral despair models of tail suspension test (TST) and forced swimming test (FST), and a chronic unpredictable mild stress (CUMS) model. CSA (30 or 60 mg/kg), intragastrically administrated for 7 days, could significantly reduce the immobility time of mice in TST and FST. CSA treatment (15 or 30 mg/kg) significantly reversed the depressive-like behavioral changes of mice induced by 3 or 6 weeks CUMS that caused the decrease of sucrose preference, the increase of latency to feed in the novelty-suppressed feeding test, and the increase of immobility time in TST of mice. Furthermore, the related mechanisms of the effect were explored by accessing the metabolite levels of kynurenine pathway of tryptophan metabolism and the expression of some related proteins in cerebral cortex of CUMS mice. Our results showed that the kynurenine pathway was upregulated after CUMS, while the alteration could be significantly reversed by CSA. CSA also reversed the CUMS-induced decrease in the levels of BDNF, PSD-95, p-Akt/Akt and p-mTOR/mTOR. Therefore, the antidepressant-like effects of CSA might be achieved through regulating tryptophan metabolism, promoting BDNF and PSD-95 expression, and activating Akt/mTOR pathway in the cerebral cortex.

The leaf of the lotus (Nelumbo nucifera) is a natural plant resource used as both food and herbal medicine (He-Ye) in China. Alkaloids are considered the major bioactive compound of the herb and exhibit various biological activities, including anti-hyperlipidemia, anti-obesity, anti-inflammatory, and anti-hyperuricemic effects. Nuciferine (NF) and N-nuciferine (N-NF) are two major alkaloids found in the herb. In the present work, the plasma and brain pharmacokinetics of the two compounds were investigated after oral and intravenous (i.v.) administration of a lotus leaf alkaloid fraction to SD rats via ultra-performance liquid chromatography coupled with photodiode array detection and brain microdialysis. After oral administration (50 mg/kg), the two compounds NF and N-NF were rapidly absorbed into the blood and reached a mean maximum concentration (Cmax) of 1.71 μg/mL at 0.9 h and 0.57 μg/mL at 1.65 h, respectively. After i.v. administration (10 mg/kg), NF and N-NF were found to have a relatively wide volume of distribution (Vd, λz, 9.48 and 15.17 L/kg, respectively) and slow elimination half-life (t1/2, λz, 2.09 and 3.84 h, respectively). The oral bioavailability of NF and N-NF was estimated as 58.13% and 79.91%, respectively. After i.v. dosing (20 mg/kg), the two compounds rapidly crossed the blood–brain barrier and reached their Cmax (in unbound form): 0.32 and 0.16 μg/mL at 0.89 and 1.22 h, respectively. Both alkaloids had widespread distribution in the brain, with Vd, λz/F-values of 19.78 L/kg and 16.17 L/kg, respectively. The mean t1/2, λz values of NF and N-NF in the brain were 1.24 and 1.39 h, respectively. These results can help us to better understand the characteristics and neuro-pharmacological effects of the lotus alkaloid fraction.

We report the observation of local superconductivity induced at the point contact formed between a normal metal tip and WC -- a triple point topological semimetal with super hardness. Remarkably, the maximum critical temperature is up to near 12 K but insensitive to the tip's magnetism. The lateral dimensions of the superconducting puddles were evaluated and the temperature dependencies of superconducting gap and upper critical field were also obtained. These results put constraints on the explanation of the induced superconductivity and pave a pathway for exploring topological superconductivity., Comment: 7 pages, 6 figures

Interfaces between materials with different electronic ground states have become powerful platforms for creating and controlling novel quantum states of matter, in which inversion symmetry breaking and other effects at the interface may introduce additional electronic states. Among the emergent phenomena, superconductivity is of particular interest. Here, by depositing metal films on a newly identified topological semimetal tungsten carbide (WC) single crystal, interfacial superconductivity is obtained, evidenced from soft point-contact spectroscopy. This very robust phenomenon is demonstrated for a wide range of metal/WC interfaces, involving both nonmagnetic and ferromagnetic films, and the superconducting transition temperatures are surprisingly insensitive to the magnetism of thin films. This method offers an opportunity to explore the long-sought topological superconductivity and has potential applications in topological-state-based spin devices.

Aims The present study aims to investigate the impacts of olfactory bulbectomy (OBX) on urinary metabolic profile and tryptophan metabolites in prefrontal cortex (PFC) of rats, and to explore the regulation effects of fluoxetine. Main methods OBX model was developed by aspiration of olfactory bulbs. After fluoxetine treatment (10 mg/kg) for 14 days, urine samples were collected and behavior tests were applied. Tryptophan (TRP) metabolites and neurotransmitters in PFC were determined by prominence ultrafast liquid chromatography-QTRAP-mass spectrometry, and tryptophan hydroxylase 2 (TPH2) and indoleamine-2,3-dioxygenase 1 (IDO1) were evaluated by western blot. Urinary metabolites were analyzed by ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry-based metabonomics strategy. Key finding OBX rats showed hyperlocomotion in open field, hyperactivity in open arm and despair status, and fluoxetine reserved these behavioral abnormalities. The levels of TRP, 5-HIAA, 5-HIAA/5-HT ratio and DA increased, while kynurenine and 5-HT decreased in PFC of OBX rats. The activities of TPH2 and IDO1were inhibited after OBX. Twenty-six altered metabolites were identified as potential biomarkers in OBX rats involved in tryptophan metabolism, gut microbiota metabolism, energy metabolism, purine metabolism, ascorbate and aldarate metabolism, and tyrosine metabolism. Among them, 15 abnormal metabolites were corrected by fluoxetine to some extent. Significance Our results revealed that urinary metabolic profile changed greatly in OBX rats, and identified biomarkers might be helpful for the diagnosis of agitated depression. The regulation effects of fluoxetine on urinary metabolic profile and tryptophan metabolites in PFC might contribute to its antidepressant action in OBX rats.

C27H26FN3O5, triclinic, P1̄ (no. 2), a = 10.8141(6) Å, b = 11.0261(6) Å, c = 11.9967(7) Å, α = 83.398(4)°, β = 65.586(3)°, γ = 81.088(4)°, V = 1284.7 Å3, Z = 2, Rgt(F) = 0.0490, wRref(F2) = 0.1519, T = 296 K.

The structural and transport properties of LaTiO3+beta/2 epitaxial thin films, grown at different oxygen pressures ranging from 6.6 x 10(-4) to 5 Pa, have been investigated. X-ray diffraction peaks of the films shift to lower angles with increasing oxygen pressure, indicative of a variation of the corresponding lattice spacing. All the films show T 2 dependence of resistivity over a large temperature range of similar to 200 K, suggesting a band-filling-induced metallic Fermi-liquid behaviour. Upturns in resistivity have been revealed at low temperatures, which could be ascribed to the Anderson-localization effect caused by the cation vacancies. Furthermore, for the thin films grown at high oxygen pressures of 0.5 and 5 Pa, the dependence of resistivity on temperature shows a maximum at high temperatures. The maximum seems to support the argument that transition between t-orbital ordering and disordering plays an important role in dominating transport properties at high temperatures. Carrier density deduced from Hall coefficient increases with the decrease of oxygen content, and shows strong temperature dependence. From the experimental data, it can be asserted that in the LaTiO3+beta/2 thin films, besides the band filling effect, localization or disorder caused by La and Ti vacancy effects controls the unique transport properties.