Preparation of VC nanoliposomes by high pressure homogenization: Process optimization and evaluation of efficacy, transdermal absorption, and stability.

Vitamin C (VC) possesses antioxidant and whitening effects. However, its effectiveness is hindered by challenges such as instability, impaired solubility, and limited bioavailability hinder. In this study, VC was encapsulated in nanoliposomes by primary emulsification and high-pressure homogenization. The VC nanoliposomes were comprehensively characterized for their microscopic morphology, particle size, polydispersity index (PDI), and encapsulation efficiency (EE). Orthogonal experiments were designed to optimize the optimal preparation process, and the antioxidant activity, whitening efficacy, transdermal absorption, and stability of VC nanoliposomes were evaluated based on this optimized process. The findings demonstrated the high reproducibility of the optimal process, with particle size, PDI, and EE values of 113.502 ± 4.360 nm, 0.104 ± 0.010, and 56.09 ± 1.01 %, respectively. Differential scanning calorimetry analysis showed effective encapsulation of VC nanoliposomes with better thermal stability than aqueous VC solution. Besides, the VC nanoliposomes demonstrated excellent antioxidant and whitening effects in efficacy experiments, stronger skin permeability in transdermal experiments and fluorescence tracking. Furthermore, storage stability tests indicated that the VC in nanoliposomes remained relatively stable after 60 days of storage. These findings highlighted the potential use of VC nanoliposomes in a wide range of applications for the cosmetic market, especially in the development of ingredients for skin care products.

Effects of Central Metal Ion on Binuclear Metal Phthalocyanine-Based Redox Mediator for Lithium Carbonate Decomposition.

Li2CO3 is the most tenacious parasitic solid-state product in lithium-air batteries (LABs). Developing suitable redox mediators (RMs) is an efficient way to address the Li2CO3 issue, but only a few RMs have been investigated to date, and their mechanism of action also remains elusive. Herein, we investigate the effects of the central metal ion in binuclear metal phthalocyanines on the catalysis of Li2CO3 decomposition, namely binuclear cobalt phthalocyanine (bi-CoPc) and binuclear cobalt manganese phthalocyanine (bi-CoMnPc). Density functional theory (DFT) calculations indicate that the key intermediate peroxydicarbonate (*C2O62-) is stabilized by bi-CoPc2+ and bi-CoMnPc3+, which is accountable for their excellent catalytic effects. With one central metal ion substituted by manganese for cobalt, the bi-CoMnPc's second active redox couple shifts from the second Co(II)/Co(III) couple in the central metal ion to the Pc(-2)/Pc(-1) couple in the phthalocyanine ring. In artificial dry air (N2-O2, 78:22, v/v), the LAB cell with bi-CoMnPc in electrolyte exhibited 261 cycles under a fixed capacity of 500 mAh g-1carbon and current density of 100 mA g-1carbon, significantly better than the RM-free cell (62 cycles) and the cell with bi-CoPc (193 cycles).

Sr-induced Fermi Engineering of ß-FeOOH for Multifunctional Catalysis.

Designing a multifunctional electrocatalyst to produce H2 from water, urea, urine, and wastewater, is highly desirable yet challenging because it demands precise Fermi-engineering to realize stronger π-donation from O 2p to electron(e- )-deficient metal (t2g ) d-orbitals. Here a Sr-induced phase transformed ß-FeOOH/α-Ni(OH)2 catalyst anchored on Ni-foam (designated as pt-NFS) is introduced, where Sr produces plenteous Fe4+ (Fe3+ → Fe4+ ) to modulate Fermi level and e- -transfer from e- -rich Ni3+ (t2g )-orbitals to e- -deficient Fe4+ (t2g )-orbitals, via strong π-donation from the π-symmetry lone-pair of O bridge. pt-NFS utilizes Fe-sites near the Sr-atom to break the H─O─H bonds and weakens the adsorption of *O while strengthening that of *OOH, toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Invaluably, Fe-sites of pt-NFS activate H2 -production from urea oxidation reaction (UOR) through a one-stage pathway which, unlike conventional two-stage pathways with two NH3 -molecules, involves only one NH3 -molecule. Owing to more suitable kinetic energetics, pt-NFS requires 133 mV (negative potential shift), 193 mV, ≈1.352 V, and ≈1.375 V versus RHE for HER, OER, UOR, and human urine oxidation, respectively, to reach the benchmark 10 mA cm-2 and also demonstrates remarkable durability of over 25 h. This work opens a new corridor to design multifunctional electrocatalysts with precise Fermi engineering through d-band modulation.

Carbon-Atom Exchange between [MC2]+ (M = Os and Ir) and Methane: on the Thermodynamic and Dynamic Aspects.

Gas-phase reactions of [OsC2]+ and [IrC2]+ with methane at ambient temperature have been studied using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. Both [OsC2]+ and [IrC2]+ undergo carbon-atom exchange reactions with methane. The associated mechanisms for the two systems are found to be similar. The differences in the rates of carbon isotope exchange reactions of methane with [MC2]+ (M = Os and Ir) are explained by several factors like the energy barrier for the initial H3C-H bond breaking processes, the molecular dynamics, orbital interactions, and the H-binding energies of the pivotal steps. Besides, the number of participating valence orbitals might be one of the keys to regulate the rate in the key step. The present findings may provide useful ideas and inspiration for designing similar processes.

General Construction of Asymmetric Amine Ethers via Efficient Transesterification.

A novel method to prepare asymmetric amine ethers is reported. Tertiary amine alcohol hydrogen sulfate intermediates are prepared through a reactive distillation process, followed by the transesterification process to afford eventually asymmetric amine ethers. Experiments and DFT calculations revealed the essential roles the sulfate group plays in the highly selective monoesterification process. This clean method is tolerant towards various functional groups with good yields under mild condition, which is obviously superior compared to the conventional processes.

Methane Activation by [AlFeO3 ]+ : the Hidden Spin Selectivity.

The performance of heteronuclear cluster [AlFeO3 ]+ in activating methane has been explored by a combination of high-level quantum chemical calculations with gas-phase experiments. At room temperature, [AlFeO3 ]+ is a mixture of 7 [AlFeO3 ]+ and 5 [AlFeO3 ]+ , in which two states lead to different reactivity and chemoselectivity for methane activation. While hydrogen extracted from methane is the only product channel for the 7 [AlFeO3 ]+ /CH4 couple, 5 [AlFeO3 ]+ is able to convert this substrate to formaldehyde. In addition, the introduction of an external electric field may regulate the reactivity and product selectivity. The interesting doping effect of Fe and the associated electronic origins are discussed, which may guide one on the design of Fe-involved catalyst for methane conversion.

Direct Conversion of Methane to Propylene.

Nonoxidative coupling of methane exhibits promising prospect in that it affords value-added hydrocarbons and hydrogen with high atom economy. However, challenge remains in direct, selective conversion of methane to more valuable hydrocarbons like olefins. The current work presents a catalyst with well-dispersed Ta atoms anchored by graphitic C3N4-supported phthalocyanine. Such a catalyst is able to convert methane selectively to ethylene and propylene at a relatively low temperature (350 °C). The conception of the active center and construction of the catalyst have been described, and the origins of the catalytic performance are discussed.

On the performance of the M-C (M = Fe, Ru, Os) unit toward methane activation.

Gas-phase reactions of [MC]+ (M = Os and Ru) with methane at ambient temperature have been studied by using quadrupole-ion trap (Q-IT) mass spectrometry combined with quantum chemical calculations. Theoretical calculations reveal the influence of electronic signatures and that it is the energy gap of the associated frontier molecular orbitals that dominates the ability of the cluster in the initial H3C-H bond breaking. By extension, a theoretical consideration upon changing the ligand from carbide to carbyne and eventually to carbene reveals that the reactivities of the M-complex (M = Os, Ru and Fe) are determined by the energy gap of the involved orbitals. In addition, a few factors like the dipole moment, spin density and charge distributions influence the orbital energy gap to different extents. Thus, altering the local structure of the active center to modulate the orbital distribution may be a possible means of regulation of the activity.

Machine Learning Design of Single-Atom Catalysts for Nitrogen Fixation.

First-principles calculations have been combined with machine learning in the design of transition-metal single-atom catalysts. Readily available descriptors are selected to describe the nitrogen activation capability of metals and coordinating atoms. Thus, a series of V/Nb/Ta-Nx single-atom catalysts are screened out as promising structures upon considering the stability, activity, and selectivity investigated computationally. Furthermore, by using the gradient boosting regression algorithm, an accurate prediction of the hydrogenation barriers for the nitrogen reduction reaction (NRR) is achievable, with a root-mean-squared error of 0.07 eV. The integration of high-throughput computation and machine learning constitutes a powerful strategy for the acceleration of catalyst design. This approach facilitates the rapid and accurate prediction of the NRR performance of more than 1000 single-atom catalyst structures. Moreover, the current work provides further insights by elaborately correlating the structure and performance, which may be instructive for both the design and application of vanadium-group catalysts.

Machine Learning Spectroscopy Using a 2-Stage, Generalized Constituent Contribution Protocol.

A corrected group contribution (CGC)-molecule contribution (MC)-Bayesian neural network (BNN) protocol for accurate prediction of absorption spectra is presented. Upon combination of BNN with CGC methods, the full absorption spectra of various molecules are afforded accurately and efficiently-by using only a small dataset for training. Here, with a small training sample (<100), accurate prediction of maximum wavelength for single molecules is afforded with the first stage of the protocol; by contrast, previously reported machine learning (ML) methods require >1,000 samples to ensure the accuracy of prediction. Furthermore, with <500 samples, the mean square error in the prediction of full ultraviolet spectra reaches <2%; for comparison, ML models with molecular SMILES for training require a much larger dataset (>2,000) to achieve comparable accuracy. Moreover, by employing an MC method designed specifically for CGC that properly interprets the mixing rule, the spectra of mixtures are obtained with high accuracy. The logical origins of the good performance of the protocol are discussed in detail. Considering that such a constituent contribution protocol combines chemical principles and data-driven tools, most likely, it will be proven efficient to solve molecular-property-relevant problems in wider fields.

Theory-Guided Construction of the Unsaturated V-N2 Site with Carbon Defects for Highly Selective Electrocatalytic Nitrogen Reduction.

Renewable energy-driven, electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia synthesis. However, improving catalyst activity and selectivity under ambient conditions has long been challenging. In this work, we obtained the potential active V-N center through theoretical prediction and successfully constructed the associated V-N2/N3 structure on N-doped carbon materials. Surprisingly, such a catalyst exhibits excellent electrocatalytic NRR performance. The V-N2 catalyst affords a remarkably high faradaic efficiency of 76.53% and an NH3 yield rate of 31.41 µgNH3 h-1 mgCat.-1 at -0.3 V vs RHE. The structural characterization and density functional theory (DFT) calculations verified that the high performance of the catalyst originates from the tuned d-band upon coordination with nitrogen, in line with the original design intention as derived theoretically. Indeed, the V-N2 center with carbon defects enhances dinitrogen adsorption and charge transfer, thereby lowering the energy barriers to form the *NNH intermediates. Such a strategy as a rational design─controllable synthesis─theoretical verification may prove effective as well for other chemical processes.

Methane Activation by [OsC3]+: Implications for Catalyst Design.

Gas-phase reactions of [OsC3]+ with methane at ambient temperature have been studied by using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. The comparison of [OsC3]+ with the product clusters revealed significant changes in cluster reactivity. In particular, with different ligands, the cluster may produce multiple products or, alternatively, just a single product. Theoretical calculations reveal the influence of electronic features such as molecular polarity index, charge and spin distribution, and HOMO-LUMO gap on the reactivity of the Os complexes. Fundamentally, it is the polarity of the clusters that leads to the cluster reactivity in the methane activation. Furthermore, reducing the local polarity of the catalyst active site may be one means of reducing the number of byproducts in the reaction.

Genome-wide association study for biomass accumulation traits in soybean.

Soybean is one of the most versatile crops for oil production, human diets, and feedstocks. The vegetative biomass of soybean is an important determinant of seed yield and is crucial for the forage usages. However, the genetic control of soybean biomass is not well explained. In this work, we used a soybean germplasm population, including 231 improved cultivars, 207 landraces, and 121 wild soybeans, to investigate the genetic basis of biomass accumulation of soybean plants at the V6 stage. We found that biomass-related traits, including NDW (nodule dry weight), RDW (root dry weight), SDW (shoot dry weight), and TDW (total dry weight), were domesticated during soybean evolution. In total, 10 loci, encompassing 47 putative candidate genes, were detected for all biomass-related traits by a genome-wide association study. Among these loci, seven domestication sweeps and six improvement sweeps were identified. Glyma.05G047900, a purple acid phosphatase, was a strong candidate gene to improve biomass for future soybean breeding. This study provided new insights into the genetic basis of biomass accumulation during soybean evolution. Supplementary information: The online version contains supplementary material available at 10.1007/s11032-023-01380-6.

V-Integration Modulates t2g -Electrons of a Single Crystal Ir1- x (Ir0.8 V0.2 O2 )x -BHC for Boosted and Durable OER in Acidic Electrolyte.

Realizing efficacious π-donation from the O 2p orbital to electron-deficient metal (t2g ) d-orbitals along with separately tuned adsorption of *O and *OOH, is an imperious pre-requisite for an electrocatalyst design to demonstrate boosted oxygen evolution reaction (OER) performance. To regulate the π-donation and the adsorption ability for *O and *OOH, herein, a facile strategy to modulate the electron transfer from electron-rich t2g -orbitals to electron-deficient t2g -orbitals, via strong π-donation from the π-symmetry lone pairs of the bridging O2- , and the d-band center of a biomimetic honeycomb (BHC)-like nanoarchitecture (Ir1- x (Ir0.8 V0.2 O2 )x -BHC) is introduced. The suitable integration of V heteroatoms in the single crystal system of IrO2 decreases the electron density on the neighboring Ir sites, and causes an upshift in the d-band center of Ir1- x (Ir0.8 V0.2 O2 )x -BHC, weakening the adsorption of *O while strengthening that of *OOH, lowers the energy barrier for OER. Therefore, BHC design demonstrates excellent OER performance (shows a small overpotential of 238 mV at 10 mA cm-2 and a Tafel slope of 39.87 mV dec-1 ) with remarkable stability (130 h) in corrosive acidic electrolyte. This work opens a new corridor to design robust biomimetic nanoarchitectures of modulated π-symmetry (t2g ) d-orbitals and the band structure, to achieve excellent activity and durability in acidic environment.

Room-Temperature Conversion of Methane to Methanediol by [FeO2].

Inspired by the activities of P-450 enzyme and Rieske oxygenases in nature, in which the high-valent Fe-oxo complexes play a key role for oxidation of alkanes, the oxidation process of methane by the high-valent iron oxide cation [FeO2]+ has been explored by using Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. In contrast to the previously reported [FeO]+/CH4 and [Fe(O)OH]+/CH4 systems, which afford [FeOH]+ as the main product, the generation of Fe+ dominates the reaction of [FeO2]+ with CH4. Theoretical calculations suggest a novel "oxygen rebound" pathway for the liberation of methanediol. In particular, the inevitable valence increase of Fe prior to C-H activation is similar to the cytochrome P-450 mediated processes. To our best knowledge, this study provides the first example of methane activation by the high-valent Fe(V)-oxo species in the gas phase, which may thus bridge the gas-phase model and the condensed-phase biosystems.

How Doping Affects the Activity of the Aluminum Oxide Support.

The performance of heteronuclear clusters [AlXO3 ]+ (X=Al, AlO4 , AlMg2 O2 , AlZnO, AlAu2 , Mg, Y, VO, NbO, TaO) in activating methane has been explored by a combination of high-level quantum calculations with reported and supplementary gas-phase experiments. With different dopants in [AlXO3 ]+ , the mechanism, reactivity and selectivity towards methane activation varies accordingly. The classic HAT competes with PCET, depending on the composition of intramolecular interactions. Although the existence of terminal oxygen radical is beneficial for classic HAT, the Alt -C interaction in the [AlXO3 ]+ clusters as enhanced by the strongly electronegative doping groups (X=Al, AlZnO, Mg, Zn, VO, NbO, TaO) favors the PCET process, facilitating C-H bond breaking. In addition, with different dopants, the destiny of the split methyl group varies accordingly. While strong interaction between Alt and CH3 results in the formation of the Alt -C bond, dopants with variable valance may promote the formation of deep-oxidation products like formaldehyde. It has been discussed in detail how to regulate the activity and selectivity of the active center of the catalyst via rational doping.

Size Effects in Gas-phase C-H Activation.

The gas-phase clusters reaction permits addressing fundamental aspects of the challenges related to C-H activation. The size effect plays a key role in the activation processes as it may substantially affect both the reactivity and selectivity. In this paper, we reviewed the size effect related to the hydrocarbon oxidation by early transition metal oxides and main group metal oxides, methane activation mediated by late transition metals. Based on mass-spectrometry experiments in conjunction with quantum chemical calculations, mechanistic discussions were reviewed to present how and why the size greatly regulates the reactivity and product distribution.

Elimination of an unfavorable allele conferring pod shattering in an elite soybean cultivar by CRISPR/Cas9.

Pod shattering can lead to devastating yield loss of soybean and has been a negatively selected trait in soybean domestication and breeding. Nevertheless, a significant portion of soybean cultivars are still pod shattering-susceptible, limiting their regional and climatic adaptabilities. Here we performed genetic diagnosis on the shattering-susceptible trait of a national registered cultivar, Huachun6 (HC6), and found that HC6 carries the susceptible genotype of a candidate Pod dehiscence 1 (PDH1) gene, which exists in a significant portion of soybean cultivars. We next performed genome editing on PDH1 gene by clustered regularly interspaced short palindromic repeats (CRISPR)-CRISPR-associated protein 9 (Cas9). In T2 progenies, several transgene-free lines with pdh1 mutations were characterized without affecting major agronomic traits. The pdh1 mutation significantly improved the pod shattering resistance which is associated with aberrant lignin distribution in inner sclerenchyma. Our work demonstrated that precision breeding by genome editing on PDH1 holds great potential for precisely improving pod shattering resistance and adaptability of soybean cultivars.

General Construction of Amine via Reduction of N=X (X = C, O, H) Bonds Mediated by Supported Nickel Boride Nanoclusters.

Amines play an important role in synthesizing drugs, pesticides, dyes, etc. Herein, we report on an efficient catalyst for the general construction of amine mediated by nickel boride nanoclusters supported by a TS-1 molecular sieve. Efficient production of amines was achieved via catalytic hydrogenation of N=X (X = C, O, H) bonds. In addition, the catalyst maintains excellent performance upon recycling. Compared with the previous reports, the high activity, simple preparation and reusability of the Ni-B catalyst in this work make it promising for industrial application in the production of amines.

Underlying Mechanisms of Reductive Amination on Pd-Catalysts: The Unique Role of Hydroxyl Group in Generating Sterically Hindered Amine.

Pd nanospecies supported on porous g-C3N4 nanosheets were prepared for efficient reductive amination reactions. The structures of the catalysts were characterized via FTIR, XRD, XPS, SEM, TEM, and TG analysis, and the mechanisms were investigated using in situ ATR−FTIR spectroscopic analysis complemented by theoretical calculation. It transpired that the valence state of the Pd is not the dominating factor; rather, the hydroxyl group of the Pd(OH)2 cluster is crucial. Thus, by passing protons between different molecules, the hydroxyl group facilitates both the generation of the imine intermediate and the reduction of the C=N unit. As a result, the sterically hindered amines can be obtained at high selectivity (>90%) at room temperature.