Synthesis, Structure, and Reactivity of Rare-Earth Metal Carboryne Complexes

Rare-earth metal carboryne complexes LRE(C2B10H10)(thf)n [n = 2, RE = Y (1a), Er (1b); n = 1, RE = Y (2); L = 2-(2,5-Me2C4H2N)C6H4NC(Ph)N(2,6-iPr2C6H3)] were synthesized in good yields via either an alkane elimination reaction of rare-earth metal dialkyls LRE(CH2SiMe3)2 with 1 equiv of o-carborane (o-C2B10H12) in THF or a salt metathesis reaction of yttrium dichloride LYCl2(thf)3 with 1 equiv of Li2C2B10H10 in toluene. They could be viewed as a class of three-membered rare-earth metallacyclopropanes. Their molecular structures were confirmed by single-crystal X-ray analyses, supporting the formation of a unique (RE)CC three-membered ring between the rare-earth metal and two cage C atoms of the carboryne moiety. They underwent ring-expansion (mono-insertion) reactions with many unsaturated organic compounds such as aldehyde, ketone, nitrile, carbodiimide, isocyanate, and thioisocyanate to give exclusively five-membered metallacycles, where the ring-strain plays an important role

Confined Nanospace Synthesis of Less Aggregated and Porous Nitrogen-Doped Graphene As Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

A facile and low-emission strategy is used for preparation of porous nitrogen-doped graphene (NGR) in a confined nanospace. The negative charged graphene oxide (GO) serves as a substrate for deposition of electropositive metal amine complex and then thin layer of silica (SiO₂) is formed onto the copper amine ion-coated GO. Carbonization of copper amine ion-coated GO in a confined nanospace of SiO₂ and the subsequent removal of the Cu particles and SiO₂ layer produces less aggregated and porous nitrogen-doped graphene (NGR). NGR materials are highly active, cheap, and selective metal-free electrocatalysts for the oxygen reduction reaction (ORR) in alkaline solution. The electron transfer for ORR at NGR catalysts is found to be around 4 at potentials ranging from −0.35 to −0.70 V. NGR may be further exploited as potentially efficient and inexpensive nonmetal ORR catalysts with good selectivity and long-term stability in alkaline solution

Proteomic Analysis of Egg Yolk Proteins During Embryonic Development in Wanxi White Goose

To investigate the alterations of yolk protein during embryonic development in Wanxi white goose, the egg yolk protein composition at days 0, 4, 7, 14, 18, and 25 of incubation (D0, D4, D7, D14, D18, and D25) was analyzed by two-dimensional gel electrophoresis combined with mass spectrometry. A total of 65 spots representing 11 proteins with significant abundance changes were detected. Apolipoprotein B-100, vitellogenin-1, vitellogenin-2-like, riboflavin-binding protein, and serotransferrin mainly participated in nutrient (lipid, riboflavin, and iron ion) transport, and vitellogenin-2-like showed a lower abundance after D14. Ovomucoid-like were involved in endopeptidase inhibitory activity and immunoglobulin binding and exhibited a higher expression after D18, suggesting a potential role in promoting the absorption of immunoglobulin and providing passive immune protection for goose embryos after D18. Furthermore, myosin-9 and actin (ACTB) were involved in the tight junction pathway, potentially contributing to barrier integrity. Serum albumin mainly participated in cytolysis and toxic substance binding. Therefore, the high expression of serum albumin, myosin-9, and ACTB throughout the incubation might protect the developing embryo. Apolipoprotein B-100, vitellogenin-1, vitellogenin-2-like, riboflavin-binding protein, and serotransferrin might play a crucial role in providing nutrition for embryonic development, and VTG-2-like was preferentially degraded/absorbed

Reactivity of 1,3-Disubstituted Indoles with Lithium Compounds: Substituents and Solvents Effects on Coordination and Reactivity of Resulting 1,3-Disubstituted-2-Indolyl Lithium Complexes

Reactivity of 1,3-disubstituted indolyl compounds with lithium reagents was studied to reveal the substituents and solvent effects on coordination modes and reactivities resulting in different indolyl lithium complexes. Treatment of 1-alkyl-3-imino functionalized compounds 1-R-3-(R′NCH)­C₈H₅N [R = Bn, R′ = Dipp (<b>HL</b>^<b>1</b>); R = Bn, R′ = ^<i>t</i>Bu (<b>HL</b>^<b>2</b>); R = CH₃OCH₂, R′ = Dipp (<b>HL</b>^<b>3</b>); Dipp = ^<i>i</i>Pr₂C₆H₃] with Me₃SiCH₂Li or ^<i>n</i>BuLi in hydrocarbon solvents (toluene or <i>n</i>-hexane) produced 1,3-disubstituted-2-indolyl lithium complexes [η¹:(μ₂-η¹:η¹)-1-Bn-3-(DippNCH)­C₈H₄NLi]₂ (<b>1</b>), {[η¹:(μ₃-η¹:η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄N]­[η²:η¹:(μ₂-η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄N]­[η¹:(μ₂-η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄N]­Li₃} (<b>2</b>), and [η¹:η¹:(μ₂-η¹:η¹)-1-CH₃OCH₂-3-(DippNCH)­C₈H₄NLi]₂ (<b>3</b>), respectively. The bonding modes of the indolyl ligand were kept in <b>1</b> by coordination with donor solvent, affording [η¹:(μ₂-η¹:η¹)-1-Bn-3-(DippNCH)­C₈H₄NLi­(THF)]₂ (<b>4</b>). The trinuclear complex <b>2</b> was converted to dinuclear form with a change of bonding modes of the indolyl ligand by treatment of <b>2</b> with donor solvent THF, producing [η¹:(μ₂-η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄NLi­(THF)]₂ (<b>5</b>). X-ray diffraction established that compounds <b>1</b>, <b>3</b>, <b>4</b>, and <b>5</b> crystallized as dinuclear structures with the carbanionic sp² carbon atoms of the indolyl ligands coordinated to lithium ions in a μ₂-η¹:η¹ manner, while compound <b>2</b> crystallized as a trinuclear structure and the carbanionic atoms of the indolyl moieties coordinated to lithium ions in μ₂-η¹:η¹ and μ₃-η¹:η¹:η¹ manners. When the lithiation reaction of <b>HL</b>^<b>1</b> with 1 equiv of ^<i>n</i>BuLi was carried out in THF, the monomeric lithium complex {η¹:η¹-1-Bn-3-(DippNCH)-2-[1′-Bn-3′-(DippNCH)­C₈H₅N]­C₈H₄NLi­(THF)} (<b>6</b>) having coupled indolyl moieties was obtained. The compound <b>6</b> can also be prepared by the reaction of <b>1</b> with 0.5 equiv of <b>HL</b>^<b>1</b> with a higher isolated yield. Accordingly, the lithium complexes [η¹:η⁴-1-Bn-3-^<i>t</i>BuNCH-2-(1′-Bn-3′-^<i>t</i>BuNCHC₈H₅N)­C₈H₄NLi­(L)] (L = THF, <b>7a</b>; L = Et₂O, <b>7b</b>) with the coupled indolyl moieties in η⁴ mode were isolated by treatment of <b>HL</b>^<b>2</b> with <b>2</b> in THF or Et₂O. All complexes were characterized by spectroscopic methods, and their structures were determined by X-ray diffraction study

Reactivity of 1,3-Disubstituted Indoles with Lithium Compounds: Substituents and Solvents Effects on Coordination and Reactivity of Resulting 1,3-Disubstituted-2-Indolyl Lithium Complexes

Reactivity of 1,3-disubstituted indolyl compounds with lithium reagents was studied to reveal the substituents and solvent effects on coordination modes and reactivities resulting in different indolyl lithium complexes. Treatment of 1-alkyl-3-imino functionalized compounds 1-R-3-(R′NCH)­C₈H₅N [R = Bn, R′ = Dipp (<b>HL</b>^<b>1</b>); R = Bn, R′ = ^<i>t</i>Bu (<b>HL</b>^<b>2</b>); R = CH₃OCH₂, R′ = Dipp (<b>HL</b>^<b>3</b>); Dipp = ^<i>i</i>Pr₂C₆H₃] with Me₃SiCH₂Li or ^<i>n</i>BuLi in hydrocarbon solvents (toluene or <i>n</i>-hexane) produced 1,3-disubstituted-2-indolyl lithium complexes [η¹:(μ₂-η¹:η¹)-1-Bn-3-(DippNCH)­C₈H₄NLi]₂ (<b>1</b>), {[η¹:(μ₃-η¹:η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄N]­[η²:η¹:(μ₂-η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄N]­[η¹:(μ₂-η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄N]­Li₃} (<b>2</b>), and [η¹:η¹:(μ₂-η¹:η¹)-1-CH₃OCH₂-3-(DippNCH)­C₈H₄NLi]₂ (<b>3</b>), respectively. The bonding modes of the indolyl ligand were kept in <b>1</b> by coordination with donor solvent, affording [η¹:(μ₂-η¹:η¹)-1-Bn-3-(DippNCH)­C₈H₄NLi­(THF)]₂ (<b>4</b>). The trinuclear complex <b>2</b> was converted to dinuclear form with a change of bonding modes of the indolyl ligand by treatment of <b>2</b> with donor solvent THF, producing [η¹:(μ₂-η¹:η¹)-1-Bn-3-(^<i>t</i>BuNCH)­C₈H₄NLi­(THF)]₂ (<b>5</b>). X-ray diffraction established that compounds <b>1</b>, <b>3</b>, <b>4</b>, and <b>5</b> crystallized as dinuclear structures with the carbanionic sp² carbon atoms of the indolyl ligands coordinated to lithium ions in a μ₂-η¹:η¹ manner, while compound <b>2</b> crystallized as a trinuclear structure and the carbanionic atoms of the indolyl moieties coordinated to lithium ions in μ₂-η¹:η¹ and μ₃-η¹:η¹:η¹ manners. When the lithiation reaction of <b>HL</b>^<b>1</b> with 1 equiv of ^<i>n</i>BuLi was carried out in THF, the monomeric lithium complex {η¹:η¹-1-Bn-3-(DippNCH)-2-[1′-Bn-3′-(DippNCH)­C₈H₅N]­C₈H₄NLi­(THF)} (<b>6</b>) having coupled indolyl moieties was obtained. The compound <b>6</b> can also be prepared by the reaction of <b>1</b> with 0.5 equiv of <b>HL</b>^<b>1</b> with a higher isolated yield. Accordingly, the lithium complexes [η¹:η⁴-1-Bn-3-^<i>t</i>BuNCH-2-(1′-Bn-3′-^<i>t</i>BuNCHC₈H₅N)­C₈H₄NLi­(L)] (L = THF, <b>7a</b>; L = Et₂O, <b>7b</b>) with the coupled indolyl moieties in η⁴ mode were isolated by treatment of <b>HL</b>^<b>2</b> with <b>2</b> in THF or Et₂O. All complexes were characterized by spectroscopic methods, and their structures were determined by X-ray diffraction study

Aldosterone exerts cytotoxic actions to cultured HUVECs.

<p>HUVECs were either left untreated (“Ctrl”), or treated with applied concentrations of aldosterone (1–1000 nM) for indicated time point, cell survival was tested by MTT assay (A and B), and cell death was tested by LDH release assay (C and D). Data were expressed as the mean ± SD. For each assay, n = 5. Experiments in this figure were repeated four times, and similar results were obtained. * p < 0.05 vs. “Ctrl” group.</p

Aldosterone induces caspase-3-dependent apoptotic death in HUVECs.

<p>HUVECs were treated with applied concentrations of aldosterone (1–1000 nM) for indicate time, cell apoptosis was evidenced by Annexin V FACS assay (A, representative FACS images were shown in lower panel), histone DNA ELISA assay (B), caspase-3 activity assay (C, lower panel) and Western blot assaying of cleavead-caspase-3 (“C-Caspase-3”) (C, upper panel). HUVECs, pre-treated with the caspase-3 inhibitor z-DVED-fmk (“ZDVED”, 25 μM)/AC-DEVD-CHO (“AC-DEVD”, 25 μM), or the pan caspase inhibitor z-VAD-fmk (“ZVAD”, 25 μM) for 1 hour, were stimulated with aldosterone (100 nM), caspase-3 activity and cell apoptosis were analyzed by the caspase-3 activity assay (D) and Annexin V FACS assay (E), respectively; Cell survival was tested by the MTT assay (F). Data were expressed as the mean ± SD. For each assay, n = 5. Experiments in this figure were repeated three times, and similar results were obtained. * p < 0.05 vs. “Ctrl” group. ^# p < 0.05 vs. aldosterone (100 nM) only group (D-F).</p

Additional file 16: of Genome-wide comparative transcriptome analysis of CMS-D2 and its maintainer and restorer lines in upland cotton

GO enrichment analysis of DEGs between A and R (XLS 2620 kb

Highly Cost-Effective Nitrogen-Doped Porous Coconut Shell-Based CO₂ Sorbent Synthesized by Combining Ammoxidation with KOH Activation

The objective of this research is to develop a cost-effective carbonaceous CO₂ sorbent. Highly nanoporous N-doped carbons were synthesized with coconut shell by combining ammoxidation with KOH activation. The resultant carbons have characteristics of highly developed porosities and large nitrogen loadings. The prepared carbons exhibit high CO₂ adsorption capacities of 3.44–4.26 and 4.77–6.52 mmol/g at 25 and 0 °C under atmospheric pressure, respectively. Specifically, the sample NC-650-1 prepared under very mild conditions (650 °C and KOH/precursor ratio of 1) shows the CO₂ uptake 4.26 mmol/g at 25 °C, which is among the best of the known nitrogen-doped porous carbons. The high CO₂ capture capacity of the sorbent can be attributed to its high microporosity and nitrogen content. In addition, the CO₂/N₂ selectivity of the sorbent is as high as 29, higher than that of many reported CO₂ sorbents. Finally, this N-doped carbon exhibits CO₂ heats of adsorption as high as 42 kJ/mol. The multiple advantages of these cost-effective coconut shell-based carbons demonstrate that they are excellent candidates for CO₂ capture

Aldosterone mainly induces C18 ceramide production in HUVECs.

<p>HUVECs were treated with applied concentrations of aldosterone (1–1000 nM) for 4 hours, total cellular ceramide level was analyzed by the DAG kinase assay, and was normalized to the untreated control (“Ctrl”) group (A), individual ceramide level was detected by LS-MS assay as described (F). HUVECs, pretreated with PDMP (10 μM), S1P (10 μM) or C6 ceramide (25 μM) for 1 hour, were stimulated with aldosterone (100 nM), cellular ceramide was analyzed (B); Cell survival was tested by MTT assay (C), and cell apoptosis was tested by the caspase-3 activity assay (D) or the Histone DNA ELISA assay (E). For each assay, n = 3. Experiments in this figure were repeated three times, and similar results were obtained. * p < 0.05 vs. “Ctrl” group. ** p < 0.05 (C-E).</p