Electrochemical water splitting for H2 production is limited by the sluggish anode oxygen evolution reaction (OER), thus using hydrazine oxidation reaction (HzOR) to replace OER has received great ...attention. Here we report the hierarchical porous nanosheet arrays with abundant Ni3N‐Co3N heterointerfaces on Ni foam with superior hydrogen evolution reaction (HER) and HzOR activity, realizing working potentials of −43 and −88 mV for 10 mA cm−2, respectively, and achieving an industry‐level 1000 mA cm−2 at 200 mV for HzOR. The two‐electrode overall hydrazine splitting (OHzS) electrolyzer requires the cell voltages of 0.071 and 0.76 V for 10 and 400 mA cm−2, respectively. The H2 production powered by a direct hydrazine fuel cell (DHzFC) and a commercial solar cell are investigated to inspire future practical applications. DFT calculations decipher that heterointerfaces simultaneously optimize the hydrogen adsorption free energy (ΔGH*) and promote the hydrazine dehydrogenation kinetics. This work provides a rationale for advanced bifunctional electrocatalysts, and propels the practical energy‐saving H2 generation techniques.
An efficient bifunctional electrocatalyst toward hydrazine‐assisted H2 production was designed by constructing the Ni3N‐Co3N heterointerfaces on Ni foam (Ni3N‐Co3N PNAs/NF). The catalyst can achieve energy‐saving hydrogen production in an overall hydrazine splitting (OHzS) unit, showing its potential for practical applications.
Designing highly active transition-metal-based electrocatalysts for energy-saving electrochemical hydrogen evolution coupled with hydrazine oxidation possesses more economic prospects. However, the ...lack of bifunctional electrocatalysts and the absence of intrinsic structure–property relationship research consisting of adsorption configurations and dehydrogenation behavior of N2H4 molecules still hinder the development. Now, a V-doped Ni3N nanosheet self-supported on Ni foam (V-Ni3N NS) is reported, which presents excellent bifunctional electrocatalytic performance toward both hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER). The resultant V-Ni3N NS achieves an ultralow working potential of 2 mV and a small overpotential of 70 mV at 10 mA cm–2 in alkaline solution for HzOR and HER, respectively. Density functional theory calculations reveal that the vanadium substitution could effectively modulate the electronic structure of Ni3N, therefore facilitating the adsorption/desorption behavior of H* for HER, as well as boosting the dehydrogenation kinetics for HzOR.
In this study, new α-indolylacrylate derivatives were synthesized by the reaction of 2-substituted indoles with various pyruvates using a Brønsted acid ionic liquid catalyst in butyl acetate solvent. ...This is the first report on the application of pyruvate compounds for the synthesis of indolylacrylates. The acrylate derivatives could be obtained in good to excellent yields. A preliminary biological evaluation revealed their promising anticancer activity (IC
50
= 9.73 μM for the compound
4l
) and indicated that both the indole core and the acrylate moieties are promising for the development of novel anticancer drugs. The Lipinski's rule and Veber's parameters were assessed for the newly synthesized derivatives.
4l
New α-indolylacrylate derivatives were synthesized by reaction of 2-substituted indoles with various pyruvates using a Brønsted acid ionic liquid catalyst in butyl acetate solvent. This is the first application of pyruvate compounds for the synthesis of indolylacrylates.
The front cover picture, provided by Minghao Li, Yanlong Gu and co‐workers, illustrates an environmentally benign medium that has emerged as a new facet of green chemistry. Dipolar and aprotic ...solvents were often used in acid‐catalyzed reactions. However, they are toxic and sometimes explosive. The sulfone‐containing imidazolium‐based Brønsted acid ionic liquid developed by Minghao Li and Yanlong Gu enables the use of an industrially acceptable and environmentally benign solvent, butyl acetate, as the reaction medium. The ionic liquid/butyl acetate biphasic system was successfully utilized in many organic reactions, which generally relied heavily on dipolar and aprotic solvents. Details of this work can be found in the full paper on pages 3342–3350 (A. El‐Harairy, Yiliqi, B. Lai, L. Vaccaro, M. Li, Y. Gu, Adv. Synth. Catal. 2019, 361, 3342–3350; DOI: 10.1002/adsc.201900246).
Designing highly active transition-metal-based electrocatalysts for energy-saving electrochemical hydrogen evolution coupled with hydrazine oxidation possesses more economic prospects. However, the ...lack of bifunctional electrocatalysts and the absence of intrinsic structure-property relationship research consisting of adsorption configurations and dehydrogenation behavior of N
H
molecules still hinder the development. Now, a V-doped Ni
N nanosheet self-supported on Ni foam (V-Ni
N NS) is reported, which presents excellent bifunctional electrocatalytic performance toward both hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER). The resultant V-Ni
N NS achieves an ultralow working potential of 2 mV and a small overpotential of 70 mV at 10 mA cm
in alkaline solution for HzOR and HER, respectively. Density functional theory calculations reveal that the vanadium substitution could effectively modulate the electronic structure of Ni
N, therefore facilitating the adsorption/desorption behavior of H* for HER, as well as boosting the dehydrogenation kinetics for HzOR.
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•Although acetal fragment was known to be susceptible to acid, We found surprisingly that, a special class of α-substituted N-arylaminoacetals, Mannich adducts of glyoxal dimethyl ...acetal, arylamines and ketones, are quite stable toward strong Brønsted acid. This led us to use successfully p-toluenesulfonic acid as the acid catalyst to synthesize a broad range of α-substituted N-arylaminoacetals.•The obtained Mannich adducts are able to react with 1,3-dicarbonyl compounds in the presence of Sc(OTf)3 catalyst. A special class of multi-substituted pyrroles were thus synthesized, which can be converted to some important heterocyclic compounds including indoles and 2-formyl-N-arrylpyrroles.
α-Substituted N-arylaminoacetals are important building blocks for organic synthesis, which can be synthesized via Mannich reaction by using glyoxal dimethyl acetal as a key precursor. As the acetal fragment was known to be susceptible to acid, in literature methods, the Mannich reaction was performed under either neutral or gently acidic conditions. As a result, only a few kinds of α-substituted N-arylaminoacetals have been synthesized via Mannich reaction until now. We found surprisingly that Mannich adducts of glyoxal dimethyl acetal, arylamines and ketones are quite stable toward strong Brønsted acid. This led us to use successfully p-toluenesulfonic acid as the acid catalyst to synthesize a broad range of α-substituted N-arylaminoacetals. The Mannich adducts could be obtained in good to excellent yields. Particularly, these products were demonstrated to be able to react with 1,3-dicarbonyl compounds in the presence of Sc(OTf)3 catalyst. A special class of multi-substituted pyrroles were thus synthesized, which can be converted to some important heterocyclic compounds including indoles and 2-formyl-N-arrylpyrroles. Dimethyl acetals of quinoline-2-carbaldehydes were also synthesized via one-pot three-component reactions of glyoxal dimethyl acetal, electron-rich anilines, and acetone.
Goat semen cryopreservation is a challenging process as it results in reduced motility, vitality, and fertility of spermatozoa after freezing. In this study, we evaluated the effects of different ...herbal extract nanoformulations (NFs) mint (MENFs), thyme (TENFs), and curcumin (CENFs), supplemented at either 50 or 100 μg into Tris-extender on the cryopreserved goat semen quality. The hydrothermal squeezing method was used for the preparation of the NFs extracts. The morphological evaluation of the NFs extracts was conducted by transmission electron microscopy. All NFs supplements improved (p < 0.05) the progressive motility, vitality, and plasma membrane integrity of sperm compared with the control extender after equilibration (5 °C for 2 h) and thawing (37 °C for 30 s), but had no effect on sperm abnormality and acrosome integrity. All NFs supplements decreased (p < 0.05) the apoptosis, malondialdehyde level, and chromatin decondensation of sperm cells, while increased (p < 0.05) the total antioxidant capacity and catalase activity in the frozen/thawed extender. Particularly, CENFs at a level of 100 μg showed improvement of sperm parameters and antioxidant status during cryopreservation of goat semen more than TENFs and MENFs. The CENFs improved the quality of goat spermatozoa in post-thawed semen in terms of preventing cryodamage and promoting the cryotolerance of spermatozoa when compared with TENFs and MENFs. Therefore, supplementation of Tris-extender with CENFs could enhance goat semen processing during cryopreservation.
•Effects of different herbal extract nanoformulations (mint, thyme, and curcumin) were evaluated on the quality of cryopreserved goat semen.•Curcumin extract improved the progressive motility, vitality, membrane integrity, apoptosis, and oxidative status of sperms.•Curcumin extract nanoformulations reduced the chromatin decondensation of goat spermatozoa.
Insect glutathione S-transferases (GSTs) serve critical roles in insecticides and other forms of xenobiotic chemical detoxification. The fall armyworm,
(J. E. Smith), is a major agricultural pest in ...several countries, especially Egypt. This is the first study to identify and characterize GST genes in
under insecticidal stress. The present work evaluated the toxicity of emamectin benzoate (EBZ) and chlorantraniliprole (CHP) against the third-instar larvae of
using the leaf disk method. The LC
values of EBZ and CHP were 0.029 and 1.250 mg/L after 24 h of exposure. Moreover, we identified 31 GST genes, including 28 cytosolic and 3 microsomal SfGSTs from a transcriptome analysis and the genome data of
. Depending on the phylogenetic analysis, sfGSTs were divided into six classes (delta, epsilon, omega, sigma, theta, and microsomal). Furthermore, we investigated the mRNA levels of 28 GST genes using qRT-PCR under EBZ and CHP stress in the third-instar larvae of
. Interestingly, SfGSTe10 and SfGSTe13 stood out with the highest expression after the EBZ and CHP treatments. Finally, a molecular docking model was constructed between EBZ and CHP using the most upregulated genes (SfGSTe10 and SfGSTe13) and the least upregulated genes (SfGSTs1 and SfGSTe2) of
larvae. The molecular docking study showed EBZ and CHP have a high binding affinity with SfGSTe10, with docking energy values of -24.41 and -26.72 kcal/mol, respectively, and sfGSTe13, with docking energy values of -26.85 and -26.78 kcal/mol, respectively. Our findings are important for understanding the role of GSTs in
regarding detoxification processes for EBZ and CHP.
Portulaca oleracea contains a wide range of chemical constituents, including flavonoids, alkaloids, polysaccharides, fatty acids, terpenoids, sterols, proteins, vitamins, and minerals. These chemical ...constituents are linked to the plant’s diverse pharmacological properties, such as antimicrobial and antioxidant activities. Therefore, this study is aimed at evaluating the effect of adding two concentrations (50 or 100 μg/mL) of Portulaca oleracea leaf ethanolic extracts in a native form (POLE) or nanoformulation (POLENF) on the antioxidant status of sperm medium to improve goat sperm freezability. Semen was evaluated postequilibration (5°C for 2 h), postthawing, and 2 h postincubation (37°C and 5% CO2). Phytochemical analysis showed the presence of 30 compounds in POLE, including phenolic acids and flavonoids and their glucosides. Total flavonoids were higher in POLE than in POLENF. Both extracts showed strong free radical scavenging capacity by the 2,2-diphenyl-1-picryl-hydrazyl-hydrate assay, which was higher for POLENF than POLE, whereas the antioxidant activity by the ferric reducing antioxidant power assay had no differences. In comparison to free extender, the addition of POLE (100 μg) or POLENF (50 and 100 μg) significantly improved sperm motility and viability postequilibration and postincubation and antioxidant status of sperm medium postthawing. All POLE and POLENF concentrations significantly improved motility, viability, membrane integrity, and apoptosis of spermatozoa postthawing. Enzyme activities of AST, ALT, and LDH in sperm medium postthawing were not affected by treatments. In comparing different types and concentrations of POLE with free extender, the addition of POLENF (100 μg/mL) to goat semen extender gave the most valuable results as an effective free radical scavenger and antiapoptotic during cryopreservation.
Dietary polyunsaturated fatty acids (PUFAs) can influence fertility in farm animals. Some evidence in mice and sheep have suggested that PUFAs may influence offspring sex ratio, which may have ...significant value for cattle production. To test this hypothesis, three groups of Holstein cows were supplemented with either 0%, 3% or 5% protected fat (PF) in the form of calcium salt of fatty acids (rich in omega-6) from 14–21 days pre-partum until conception. Proven-fertile frozen semen from the same ejaculate was used for insemination. Calf sex recorded at birth was 8/19 (42.1%) male offspring in the control group, increasing to 14/20 (70%, P > 0.05) and 17/20 (85%, P < 0.05) in 3% and 5% PF, respectively. To test if this effect was caused by a direct influence on the oocyte, we supplemented bovine cumulus oocyte complexes during in vitro maturation with either omega-3 alpha-linolenic acid (ALA), omega-6 linoleic acid (LA) or trans-10, cis-12 conjugated linoleic acid (CLA). Sex ratio of the produced transferable embryos was determined using PCR of SRY gene. Similar to the in vivo results, sex ratio was skewed to the male side in the embryos derived from LA- and CLA-treated oocytes (79% and 71%) compared to control and ALA-treated oocytes (44% and 54%, respectively). These results indicate that both dietary and in vitro supplementation of omega-6 PUFAs can skew the sex ratio towards the male side in cattle. Further experiments are required to confirm this effect on a larger scale and to study the mechanisms of action that might be involved.
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