In situ self-assembly of molybdenum carbide and iron carbide heterostructures on N-doped carbon for an efficient oxygen reduction reaction.

Identifying highly stable, cost-effective, platinum-free, and efficient electrocatalysts for the oxygen reduction reaction (ORR) remains a formidable challenge. The ORR is important for advancing fuel cell and zinc-air battery (ZAB) technologies towards cost-efficiency and environmental sustainability. This work presents the utilization of economically viable materials through a straightforward synthesis process, exhibiting the development of efficient Mo2C/Fe3C-NC catalysts ingeniously derived from phosphomolybdic acid (PMA) and iron phthalocyanine (FePc). The results demonstrate that the optimized Mo2C/Fe3C-NC3 catalysts exhibit remarkable electrochemical performance, evidenced by an impressive onset potential of ∼1.0 V versus RHE, a half-wave potential of 0.89 V, and a superior current density of about 6.2 mA cm-2. As for their performance in ZABs, the optimized catalysts reach a peak power density of 142 mW cm-2 at a current density of 200 mA cm-2. This synergy, coupled with the uniform distribution of Mo2C and Fe3C nanoparticles, greatly enhances the active catalytic sites and promotes electrolyte diffusion. Our approach diverges from traditional methods by employing an in situ self-assembled heterostructure of Mo2C/Fe3C on nitrogen-doped carbon tubes, avoiding the conventional high-temperature hydrogen gas reduction process. Beyond serving as feasible alternatives to commercially available Pt/C catalysts, these materials hold promise for large-scale production owing to their affordability and the simplicity of the synthesis technique. Such a breakthrough paves the way towards the realization of sustainable energy technologies and lays the groundwork for further exploration into amplifying the scalability and efficiency of ORR catalysts.

Discovery of Alkyl Triphenylphosphonium Pinostrobin Derivatives as Potent Anti-Breast Cancer Agents.

Pinostrobin demonstrated anticancer properties, but its hydrophobic feature led to a reduction in bioavailability. The mitochondria-targeted approach successfully synthesized eight new alkyl triphenylphosphonium pinostrobin derivatives (1-8) with good yield in this study. Seven compounds (1-3, 5-8) showed greater cytotoxic potency against the human MCF-7 breast cancer cell line than pinostrobin. Molecular docking studies were performed with two important targets in hormone-dependent anticancer strategies, estrogen receptor α (ERα) ligand binding domains, 3ERT (antagonist recognition and antiproliferative function), and 1GWR (agonist recognition and pro-proliferative function). In addition, the MD simulation study of the two most potent compounds (2 and 3) complexed with both ERα forms suggested that compounds 2 and 3 could serve as favourable antagonists. Furthermore, the in silico ADMET prediction indicated that compounds 2 and 3 could be potential drug candidates.

Unraveling the Electrocatalytic Activity in HMF Oxidation to FDCA by Fine-Tuning the Degree of NiOOH Phase Over Ni Nanoparticles Supported on Graphene Oxide.

The development of an efficient electrocatalyst for HMF oxidation to FDCA has been in the early stages. Herein, the NiNPs/GO-Ni-foam is fabricated as an electrocatalyst for FDCA production. However, the electrocatalytic performance of the untreated NiNPs/GO-Ni-foam is observed with moderate Faradaic efficiency (FE) (73.0%) and FDCA yield (80.2%). By electrochemically treating the NiNPs/GO-Ni-foam in an alkaline solution with positive potential at different treatment durations, the degree of NiOOH on metal surfaces is changed. The distinctive electrocatalytic activity obtained when using the different NiOOH degrees allows to understand the crucial impact of NiOOH species in HMF electrooxidation. Enhancing the portion of the NiOOH phase on the electrocatalyst surface improves electrocatalytic activity in terms of FE and FDCA yield up to 94.8±4.8% and 86.9±4.1%, respectively. Interestingly, as long as the NiOOH portion on the electrocatalyst surface is preserved or regenerated, the electrocatalyst performance can be intact even after several catalytic cycles. The theoretical study via density functional theory (DFT) also agrees with the experimental observations and confirms that the NiOOH phase facilitates the electrochemical transformation of HMF to FDCA through the HMFCA pathway, and the potential limiting step of the overall reaction is the oxidation of FFCA to FDCA.

Detailed discussion on the structure of alloy nanoparticles synthesized via magnetron sputter deposition onto liquid poly(ethylene glycol).

This paper is devoted to reviewing a decade of the development of vacuum sputter deposition onto liquid poly(ethylene glycol) (PEG) to prepare metal and alloy nanoparticles (NPs) with a controlled particle growth, size, structure, and composition. Especially, we have discussed the fine structures of alloy NPs obtained in PEG and compared them with those sputtered onto other non-volatile liquids. Finally, we have shared our prospect of applications for the resulting alloy NPs.

In vitro biological evaluation and in silico studies of linear diarylheptanoids from Curcuma aromatica Salisb. as urease inhibitors.

Plants of the Zingiberaceae family, specifically those belonging to the Curcuma species, are commonly under consideration as potential therapeutic agents for the management of gastrointestinal diseases. In this study, we carried out a phytochemical study on Curcuma aromatica Salisb. (or so-called "Nghe trang" in Vietnamese) grown in Vietnam, which yields three newly discovered 3,5-diacetoxy diarylheptanoids (1-3) and six known 3,5-dihydroxyl diarylheptanoids (4-9). The bioactivity assessment shows that all isolated compounds, except compounds 3, 7, and 8, could inhibit urease. Compounds 4 and 9 significantly inhibit urease, with an IC50 value of 9.6 and 21.4 µM, respectively, more substantial than the positive control, hydroxyurea (IC50 = 77.4 µM). The structure-activity relationship (SAR) of linear diarylheptanoids was also established, suggesting that the hydroxyl groups at any position of skeleton diarylheptanoids are essential for exerting anti-urease action. Through a comparative analysis of the binding sites of hydroxyurea and diarylheptanoid compounds via our constructed in silico model, the mechanism of action of diarylheptanoid compounds is predicted to bind to the dynamic region close to the dinickel active center, resulting in a loss of catalytic activity. Such insights certainly help design and/or find diarylheptanoid-based compounds for treating gastric ulcers through inhibiting urease.

3D Hierarchical MOF-Derived Defect-Rich NiFe Spinel Ferrite as a Highly Efficient Electrocatalyst for Oxygen Redox Reactions in Zinc-Air Batteries.

The strategy of defect engineering is increasingly recognized for its pivotal role in modulating the electronic structure, thereby significantly improving the electrocatalytic performance of materials. In this study, we present defect-enriched nickel and iron oxides as highly active and cost-effective electrocatalysts, denoted as Ni0.6Fe2.4O4@NC, derived from NiFe-based metal-organic frameworks (MOFs) for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). XANES and EXAFS confirm that the crystals have a distorted structure and metal vacancies. The cation defect-rich Ni0.6Fe2.4O4@NC electrocatalyst exhibits exceptional ORR and OER activities (ΔE = 0.68 V). Mechanistic pathways of electrochemical reactions are studied by DFT calculations. Furthermore, a rechargeable zinc-air battery (RZAB) using the Ni0.6Fe2.4O4@NC catalyst demonstrates a peak power density of 187 mW cm-2 and remarkable long-term cycling stability. The flexible solid-state ZAB using the Ni0.6Fe2.4O4@NC catalyst exhibits a power density of 66 mW cm-2. The proposed structural design strategy allows for the rational design of electronic delocalization of cation defect-rich NiFe spinel ferrite attached to ultrathin N-doped graphitic carbon sheets in order to enhance active site availability and facilitate mass and electron transport.

A new apotirucallane-type protolimonoid from the leaves of Paramignya trimera.

This study presents a phytochemical analysis of the leaves of Paramignya trimera, revealing the isolation of a new apotirucallane-type protolimonoid, identified as 25-O-methyl-1,2-dihydroprotoxylocarpin D (1), along with two known compounds (2 and 3). The known compounds were identified as (20S,21R,23R)-21,23-epoxy-7α,24,25-trihydroxy-21-O-methyl-3-oxoapotirucalla-14-ene (2) and 7α,24,25-trihydroxy-3-oxoapotirucalla-14-en-21,23-olide (3). The three apotirucallane-type protolimonoids (1-3) did not exhibit cytotoxicity against MCF-7 cells at a concentration of 100 µM. Interestingly, when MCF-7 cells were treated with compound 1 at various concentrations, a notable stimulatory response was observed, leading to a significant increase in cell viability, up to 127%.

A novel diphenylbutenoid-type compound from the rhizomes of Zingiber montanum (J.Koenig) Link ex A.Dietr. (Zingiberaceae).

From the EtOAc-soluble extract of the rhizomes of Zingiber montanum (J.Koenig) Link ex A.Dietr., a novel diphenylbutenoid, montadinin A (1) and a previously unreported phenylbutenoid compound, 1-(3,4-dimethoxyphenyl)but-3-en-2-ol (7), in natural source were isolated. Additionally, seven known phenylbutenoids were also identified. The structures of all compounds were elucidated through NMR spectroscopic interpretation. Compounds cis-3-(3,4-dimethoxyphenyl)-4-[(E)-3,4-dimethoxystyryl]cyclohex-1-ene (2), cis-4-[(E)-3,4-dimethoxystyryl]-3-(2,4,5-trimethoxyphenyl)cyclohex-1-ene (3), trans-3-(3,4,-dimethoxyphenyl)-4-[(E)-2,4,5-trimethoxystyryl]cyclohex-1-ene (5), and cis-3-(3,4-dimethoxyphenyl)-4-[(Z)-2,4,5-trimethoxylstyryl]cyclohex-1-ene (6) showed weak cytotoxicity against HepG2 cells with IC50 values of 122.9, 127.3, 257.5, and 168.5 µM, respectively.

Correction: Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co-Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc-air batteries.

Correction for 'Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co-Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc-air batteries' by Mohan Gopalakrishnan et al., Nanoscale, 2022, 14, 17908-17920, https://doi.org/10.1039/D2NR04933C.

Taxotrophises A and B, two new polyphenols from the stems of Taxotrophis ilicifolius.

From the EtOAc extract of the wood of the stems of Taxotrophis ilicifolius (Moraceae), two new secondary metabolites, named taxotrophises A (1) and B (2), were isolated, together with five known compounds (3-7). Their chemical structures have been elucidated by extensive NMR spectroscopic analysis. All isolated compounds have been evaluated for α-glucosidase inhibitory activity. In the present work, compounds 1 and 4 showed the strongest α-glucosidase inhibitory activity with IC50 values of 6.5 and 1.5 µM, respectively, and stronger than that of a positive control, acarbose (IC50; 214.5 µM).

Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co-Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc-air batteries.

Due to their affordability and good catalytic activity for oxygen reactions, MOF-derived carbon composites containing metal alloys have piqued interest. However, during synthesis, MOFs have the disadvantage of causing significant carbon evaporation, resulting in a reduction of active sites and durability. This study proposes tailoring the molecular structure of MOFs by optimizing bipyridine and flexible 4-aminodiacetic terephthalic acid ligands, which have numerous coordination modes and framework structures, resulting in fascinating architectures. MOF frameworks having optimized N and O units are coordinated with Co and Ni ions to provide MOF precursors that are annealed at 700 °C in argon. The MOF-derived Co9S8/Co-Nx/CoNi/Ni3S2@CNS-4 catalyst exhibits excellent catalytic activity, revealing an ORR half-wave potential of 0.86 V and an overpotential (OER) of 196 mV at 10 mA cm-2, a potential gap of 0.72 V and a Tafel slope of 79 mV dec-1. The proposed strategy allows for the rational design of N-coordinated Co and CoNi alloys attached to ultrathin N, S co-doped graphitic carbon sheets to enhance bifunctional activity and sufficient active sites. Consequently, the zinc-air battery using the synthesized catalyst shows a high peak power density of 206.9 mW cm-2 (Pt/C + RuO2 116.1 mW cm-2), a small polarization voltage of 0.96 V after 370 h at 10 mA cm-2, and an outstanding durability of over 2400 cycles (400 h). The key contributions to the superior performance are the synergetic effects of the CoNi alloys plus the N,S-incorporated carbon skeleton, due to the small charge transfer resistances and enhanced active sites of CoNi, metal-S, and pyridinic N.

Two new phenylbutenoids from the rhizomes of cassumunar ginger and their α-glucosidase inhibitory activity.

An extract from the rhizomes of Cassumunar ginger (Zingiber purpureum Roscoe). was found to have significant α-glucosidase inhibitory activity with an IC50 value of 6.3 µg/mL. Two new phenylbutenoids, cassudimin A (1) and cassumunol N (2), and seven known compounds (3-9) were isolated. Their structures and relative configurations of two new compounds were elucidated based on spectra interpretation. Compounds 1-3, 6-9 showed more potent α-glucosidase inhibitory activity than a positive control, acarbose (IC50 = 168.0 µM). Dehydrozingerone (6) exhibited the most potent α-glucosidase inhibition with an IC50 value of 8.3 µM. Compounds 7 and 9 were found in Z. purpureum rhizomes for the first time.

A New abeo-Icetexane-Type Diterpenoid from the Stem Barks of Taxus wallichiana.

From a CH2 Cl2 -soluble fraction of the stem barks of Taxus wallichiana, one new abeo-icetexane-type diterpenoid, taxamairin I (1), was isolated. Its absolute configuration was elucidated based on spectroscopic interpretation and time-dependent density functional theory (TD-DFT) calculation of optical rotation. In addition, the plausible biosynthesis pathway for the formation of the new abeo-icetexane-type diterpenoid was proposed. Taxamairin I (1), at a concentration of 100 µM, did not show cytotoxicity against Hep3B human liver cancer cell lines.

Injectable Fiducial Marker for Image-Guided Radiation Therapy Based on Gold Nanoparticles and a Body Temperature-Activated Gel-Forming System.

Injectable fiducial markers are crucial in image-guided radiation therapy (IGRT) due to their minimally invasive operations and improved patient compliance. This study presents the development of a ready-to-use injectable fiducial marker utilizing alginate stabilized-gold nanoparticles (alg-Au NPs) and a body temperature-activated in situ gel-forming system. Gram-scale alg-Au NPs were prepared in an hour by a green microwave-induced plasma-in-liquid process (MWPLP). Sodium alginate was introduced in this process to avoid aggregation between Au NPs, which ensured their stability and injectability. The gelation behavior of alginate with divalent cations and a temperature-dependent release of calcium source (glucono-delta-lactone (GDL) and CaCO3) served as the foundation of the body temperature-activated in situ gel-forming system. The injectable fiducial marker GDL/CaCO3/alg-Au NPs could maintain a liquid state at a low temperature for a higher injectability. After injection, on the other hand, Ca2+ would be released due to the body temperature-activated hydrolysis of GDL and the subsequent reaction with CaCO3, which would initiate the gelation of alginate. The injectable fiducial marker can be therefore delivered via injection and form gel at target site to avoid marker movement or Au NPs leakage after injection. Rheological measurements demonstrate the stability and gelation behavior of GDL/CaCO3/alg-Au NPs at different temperatures. Furthermore, the injectability and imaging ability of GDL/CaCO3/alg-Au NPs were also examined. In summary, ready-to-use injectable fiducial marker GDL/CaCO3/alg-Au NPs were developed via a green and facile method for IGRT.

Paratrimerin Z, an undescribed chromene derivative from the roots of Paramignya trimera.

From an EtOAc-soluble fraction of the roots of Paramignya trimera, one undescribed chromene derivative, paratrimerin Z (1), was isolated. Its structure was elucidated on the basis of NMR spectroscopic interpretation. The absolute configuration of 1 was determined by the specific rotation analysis of its acid-catalyzed hydrolysis product. Paratrimerin Z (1), at a concentration of 100 µM, did not show cytotoxicity against Hep3B human liver cancer cell line.

Combinatorial CRISPR Interference Library for Enhancing 2,3-BDO Production and Elucidating Key Genes in Cyanobacteria.

Cyanobacteria can convert CO2 to chemicals such as 2,3-butanediol (2,3-BDO), rendering them promising for renewable production and carbon neutralization, but their applications are limited by low titers. To enhance cyanobacterial 2,3-BDO production, we developed a combinatorial CRISPR interference (CRISPRi) library strategy. We integrated the 2,3-BDO pathway genes and a CRISPRi library into the cyanobacterium PCC7942 using the orthogonal CRISPR system to overexpress pathway genes and attenuate genes that inhibit 2,3-BDO formation. The combinatorial CRISPRi library strategy allowed us to inhibit fbp, pdh, ppc, and sps (which catalyzes the synthesis of fructose-6-phosphate, acetyl-coenzyme A, oxaloacetate, and sucrose, respectively) at different levels, thereby allowing for rapid screening of a strain that enhances 2,3-BDO production by almost 2-fold to 1583.8 mg/L. Coupled with a statistical model, we elucidated that differentially inhibiting all the four genes enhances 2,3-BDO synthesis to varying degrees. fbp and pdh suppression exerted more profound effects on 2,3-BDO production than ppc and sps suppression, and these four genes can be repressed simultaneously without mutual interference. The CRISPRi library approach paves a new avenue to combinatorial metabolic engineering of cyanobacteria.

Sputter-Deposited Binder-Free Nanopyramidal Cr/γ-Mo2N TFEs for High-Performance Supercapacitors.

Due to their outstanding power density, long cycle life and low cost, supercapacitors have gained much interest. As for supercapacitor electrodes, molybdenum nitrides show promising potential. Molybdenum nitrides, however, are mainly prepared as nanopowders via a chemical route and require binders for the manufacture of electrodes. Such electrodes can impair the performance of supercapacitors. Herein, binder-free chromium (Cr)-doped molybdenum nitride (Mo2N) TFEs having different Cr concentrations are prepared via a reactive co-sputtering technique. The Cr-doped Mo2N films prepared have a cubic phase structure of γ-Mo2N with a minor shift in the (111) plane. While un-doped Mo2N films exhibit a spherical morphology, Cr-doped Mo2N films demonstrate a clear pyramid-like surface morphology. The developed Cr-doped Mo2N films contain 0-7.9 at.% of Cr in Mo2N lattice. A supercapacitor using a Cr-doped Mo2N electrode having the highest concentration of Cr reveals maximum areal capacity of 2780 mC/cm2, which is much higher than that of an un-doped Mo2N electrode (110 mC/cm2). Furthermore, the Cr-doped Mo2N electrode demonstrates excellent cycling stability, achieving ~ 94.6% capacity retention for about 2000 cycles. The reactive co-sputtering proves to be a suitable technique for fabrication of binder-free TFEs for high-performance energy storage device applications.

Efficient iron-cobalt oxide bifunctional electrode catalysts in rechargeable high current density zinc-air batteries.

Iron-cobalt (FeCo) oxides dispersed on reduced graphene oxide (rGO) were synthesized from nitrate precursors at loading levels from 10 wt% to 60 wt%. These catalysts were tested in lab-scale zinc-air batteries (ZABs) at a high current density of 100 mA cm-2 of the cathode area for the first time, cycling between 60 min of discharging and 60 min of charging. The optimum loading level for the best ZAB cycling performance was found to be 40 wt%, at which CoFe2O4 and CoO nanocrystals were detected. A discharge capacity of at least 90% was maintained for about 60 cycles with FeCo 40 wt%, demonstrating superior stability over amorphous FeCo oxides with FeCo 10 wt% despite similar performance at electrochemical tests. At a high current density of 100 mA cm-2, OER catalytic activity was found to be the limiting factor in ZAB's cyclability. The discrepancies between the ORR/OER catalytic activities by electrochemical and battery cycling test results highlight the role and importance of rGO in improving electrical conductivity and activation of metal oxide electrocatalysts under high current density conditions. The difference of battery cycling test results from traditional electrochemical test results suggests that electrochemical tests conducted at low current densities may be inadequate in predicting practical battery cycling performance.

Anisotropic Growth of Copper Nanorods Mediated by Cl- Ions.

Anisotropic growth to form Cu particles of rod and wire shapes has been obtained typically in a complex system that involves both organic capping agents and Cl- ions. However, the sole effect of Cl- ions on the formation of Cu wires has yet to be fully understood, especially in an organic system. This present work determines the effect of Cl- ions on the morphologies of Cu particles in an organic phase without any capping agents. The results revealed that anisotropic Cu rods could be grown with the sole presence of Cl- ions. The rods have the (011) facets as the long axis, the (111) facets as the tip, and the (100) facets as the side surface. By increasing the Cl- ion concentration, more Cu atoms contributed to the formation of Cu rods and the kinetic growth of the length and the diameter of the rods varied. This suggests that Cl- ions have preferential adsorption on the (100) Cu surfaces to promote the anisotropic growth of Cu. Meanwhile, the adsorption of Cl- to the (111) and (100) surfaces at high Cl- concentrations regulates the relative growth of the particle length and diameter.

Alginate-Stabilized Gold Nanoparticles Prepared Using the Microwave-Induced Plasma-in-Liquid Process with Long-Term Storage Stability for Potential Biomedical Applications.

A one-step preparation of alginate-stabilized gold nanoparticles (Au NPs) using the microwave-induced plasma-in-liquid process (MWPLP) was reported. Effects of alginate with various concentrations on the preparation and properties of the synthesized Au NPs, including reaction rate, morphology, size, and optical absorption property, were studied. The introduction of alginate (1) accelerated the reaction rate, (2) prevented aggregation and precipitation due to long time discharge in MWPLP, and (3) provided long-term colloidal stability. An abnormal size change (from large to small) of Au NPs during particle growth, which was opposite to the typical change in bottom-up chemical reduction, was observed and a possible mechanism was proposed based on the dynamical and thermodynamical instability of particles during growth. The strategy of drying and redispersion of Au NPs in alginate solution was also studied. The drying and redispersion process had an imperceptible effect on the Au NPs. As a consequence, this strategy might be an effective technique for the long-term storage of Au NPs and other metal NPs. The alginate-stabilized Au NPs without the addition of toxic reducing or stabilizing agents can be appropriate to biomedical applications.