Embedding Double Transition Metal Atoms in B‑Modified Two-Dimensional Carbon-Rich Conjugated Frameworks for Efficient Ammonia Synthesis

It is important to develop an efficient green catalyst for electrochemical nitrogen reduction under environmental conditions to replace the Haber–Bosch process with high energy consumption, limited economic scale of production, and high CO2 emissions, but there are still some difficulties in its development and design. In this work, based on 2D CCFs, a B-modified rectangular-shaped expanded phthalocyanine bimetallic atomic catalyst is proposed. Because both the TM-d orbital and the B-sp3 hybrid orbital can accept the lone pair and feedback electrons of N2, and there are significantly different valence electron distributions between the two different metals and boron, this catalyst not only keep the advantages of metal catalysts but also play the role of the B atom to further increase the polarity of nitrogen and activate N2. In order to evaluate the catalytic performance of this catalyst, its stability, activity, selectivity, reactivity, and other aspects are screened and analyzed by density functional theory calculation. Among them, the FeNb-BPc CCF catalyst has better N2 adsorption capacity under ambient conditions, exhibits excellent catalytic activity through a continuous mechanism, and has a lower limiting potential of −0.24 V. We believe that this work opens a new path for the rational design of efficient N2 reduction reaction catalysts and also provides a theoretical basis for experimental development

Table_1_Integrated bioinformatics and machine learning algorithms reveal the critical cellular senescence-associated genes and immune infiltration in heart failure due to ischemic cardiomyopathy.docx

Heart failure (HF) is the final stage of many cardiovascular illnesses and the leading cause of death worldwide. At the same time, ischemic cardiomyopathy has replaced valvular heart disease and hypertension as the primary causes of heart failure. Cellular senescence in heart failure is currently receiving more attention. In this paper, we investigated the correlation between the immunological properties of myocardial tissue and the pathological mechanisms of cellular senescence during ischemic cardiomyopathy leading to heart failure (ICM-HF) using bioinformatics and machine learning methodologies. Our goals were to clarify the pathogenic causes of heart failure and find new treatment options. First, after obtaining GSE5406 from the Gene Expression Omnibus (GEO) database and doing limma analysis, differential genes (DEGs) among the ICM-HF and control groups were identified. We intersected these differential genes with cellular senescence-associated genes (CSAG) via the CellAge database to obtain 39 cellular senescence-associated DEGs (CSA-DEGs). Then, a functional enrichment analysis was performed to elucidate the precise biological processes by which the hub genes control cellular senescence and immunological pathways. Then, the respective key genes were identified by Random Forest (RF) method, LASSO (Least Absolute Shrinkage and Selection Operator) algorithms, and Cytoscape’s MCODE plug-in. Three sets of key genes were taken to intersect to obtain three CSA-signature genes (including MYC, MAP2K1, and STAT3), and these three CSA-signature genes were validated in the test gene set (GSE57345), and Nomogram analysis was done. In addition, we assessed the relationship between these three CSA- signature genes and the immunological landscape of heart failure encompassing immunological infiltration expression profiles. This work implies that cellular senescence may have a crucial role in the pathogenesis of ICM-HF, which may be closely tied to its effect on the immune microenvironment. Exploring the molecular underpinnings of cellular senescence during ICM-HF is anticipated to yield significant advances in the disease’s diagnosis and therapy.</p

Acylation of caveolin-1.

<p>CHO cells were cultured in Ham’s F-12 complete medium to 80% confluency. The cells were starved and then labeled with 2.5 mCi of ³H-palmitic acid or 25 µCi of ¹⁴C-stearic acid for 3 h at 37°C in the presence/absence of 30 times of non-labeled palmitic acid (C16∶0), stearic acid (C18∶0) or oleic acid (C18∶1). The cells were harvested in MBST/OG buffer and immunoprecipitated with anti-acveolin-1 IgG/protein A. The immunoprecipitated caveolin-1 was separated by SDS-PAGE, transferred to a membrane and the fatty acid associated with caveolin-1 was detected with autoradiogram. The experiments were repeated three times, and representative data are shown.</p

Quantification of fatty acids bound to caveolin-1, associated with caveolae, and present in CHO cells.

<p>The CHO cells were cultured in Ham’s F-12 medium to 90% confluency. After washed with PBS, they were dissolved in MBST/OG on ice. Post nuclear supernatant (PNS), cytosol (Cyto), internal membranes (IM), plasma membrane (PM), and caveolae (CM) were isolated with Opti-Prep method. Total fatty acids were extracted from each sample with Folch reagent, methyl esterified with BF3, and then subjected to GC/MS equipped with Omegawax 250 capillary column. Fatty acids bound to caveolin-1 (A), associated with caveolae (B), and present in CHO cells (C) were identified by MS. (D) Isolation of caveolae from CHO cells. Subcellular fractions were isolated with Opti-Prep method and subjected to Western blot using antibody against caveolin-1. (E) Immunoprecipitation of caveolin-1. The CHO cell lysates were immunoprecipitated with anti-caveolin-1 IgG/protein A-Sepharose beads and detected by Western blot using antibody against caveolin-1. The experiments were repeated three times with triplicate measurements. Quantitative analysis of the data is shown in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0060884#pone-0060884-g003" target="_blank">Figure 3</a>.</p

Grape Seed Proanthocyanidins: Novel Coloring, Flame-Retardant, and Antibacterial Agents for Silk

Grape skins and seeds rich in polyphenolic compounds are low-value byproducts from the wine-making. The valorization of such byproducts is of great significance. This work presented a novel application of grape seed proanthocyanidins (GSPs) in the dyeing and flame-retardant and antibacterial treatment of silk. The study on adsorption isotherms revealed that multiple interactions occurred between GSPs and silk, including electrovalent bonding, hydrogen bonding, and van der Waals forces. The color depth of silk mainly depended on temperature and GSP concentration. Dyed silk had acceptable color fastness to washing, rubbing, and perspiration. Postmordanting could improve light fastness. Changes in the tensile strength and flexural rigidity of dyed silk were in an acceptable range. A low concentration of GSPs imparted a durable antibacterial function to silk. The biggest highlight of this study was the improved flame retardancy of silk caused by GSP dyeing. GSPs increased the thermal stability and charring ability of silk at high temperatures, and their flame-retardant action worked in the solid phase. Mordanting had no substantial impact on the flame-retardant and antibacterial functions of dyed silk. The present research reveals that the valorization of GSPs for silk processing is feasible

Separation of fatty acid methyl esters and determination of the sensitivity and linear range of GC/MS method.

<p>A mixture of standard fatty acid esters was subjected to GC/MS equipped with Omegawax 250 capillary column. Fatty acids were identified by mass spectrometer and quantified by FID. The measurement of fatty acid methyl esters with GC/MS was of high sensitivity, up to 40 pg of tricosanoic methyl ester, and had a wide linear range, up to 10 ng (inner figure, a and b).</p

Quantification of fatty acids bound to caveolin-1, associated with caveolae, and present in CHO cells.

<p>The CHO cells were cultured in Ham’s F-12 medium to 90% confluency. Caveolae were isolated with Opti-Prep method and caveolin-1 was purified by immunoprecipitation. Total fatty acids were extracted from each sample with Folch reagent, methyl esterified with BF3, and then subjected to GC/MS equipped with Omegawax 250 capillary column. Fatty acids bound to caveolin-1 (A), associated with caveolae (B), and present in CHO cells (C) were quantified with FID. The experiments were repeated three times with triplicate measurements. Data are presented as Mean ± SD.</p

Effect of fatty acids on caveolin-1 subcellular location.

<p>CHO cells were cultured in Ham’s F-12 complete medium to 80% confluency. The cells were culture for 24 h with Ham’s F-12 containing 20% FBS, 1% BSA (fatty acid free), 1% BSA plus 200 µg/ml palmitic acid or 1% BSA plus 200 µg/ml stearic acid. The subcellular fractions were isolated with Opti-Prep method and subjected to Western blot using antibody against caveolin-1. The experiments were repeated two times and representative data are shown.</p

Insight into the reaction mechanism of ethanol steam reforming catalysed by Co–Mo₆S₈

The production of hydrogen via steam reforming of ethanol (SRE) is favourable for the use of hydrogen as an alternative fuel. Co–Mo6S8 possesses high activity and stability for SRE to sustainably produce hydrogen. The competition among reaction pathways related to C–H, O–H, C–C, C–O cleavage and H2 formation was studied. The adsorption and reaction of related intermediates in the ESR reaction pathway are described. The results indicated that the most feasible route for the decomposition of ethanol catalysed by Co–Mo6S8 is CH3CH2OH*→CH3CH2O*→CH3CHO*→CH2CHO*→CHCHO*→CHCO*→CH*+CO*. The CH* can be decomposed into C*+H*, and CO* can be oxidised via the redox mechanism of the water gas shift (WGS) reaction. Thus the final products are CO2 and H2. The present result may help people to design an SRE catalyst, which has the ability to break C–C to form CO and H2, then CO react with H2O in the WGS reaction generating CO2 and H2.</p