Quantitative analysis of the quality constituents of Lonicera japonica Thunberg based on Raman spectroscopy.

Quantitative analysis of the quality constituents of Lonicera japonica (Jinyinhua [JYH]) using a feasible method provides important information on its evaluation and applications. Limitations of sample pretreatment, experimental site, and analysis time should be considered when identifying new methods. In response to these considerations, Raman spectroscopy combined with deep learning was used to establish a quantitative analysis model to determine the quality of JYH. Chlorogenic acid and total flavonoids were identified as analysis targets via network pharmacology. High performance liquid chromatograph and ultraviolet spectroscopy were used to construct standard curves for quantitative analysis. Raman spectra of JYH extracts (1200) were collected. Subsequently, models were built using partial least squares regression, Support Vector Machine, Back Propagation Neural Network, and One-dimensional Convolutional Neural Network (1D-CNN). Among these, the 1D-CNN model showed superior prediction capability and had higher accuracy (R2 = 0.971), and lower root mean square error, indicating its suitability for rapid quantitative analysis.

Zero-determinant strategy in stochastic Stackelberg asymmetric security game.

In a stochastic Stackelberg asymmetric security game, the strong Stackelberg equilibrium (SSE) strategy is a popular option for the defender to get the highest utility against an attacker with the best response (BR) strategy. However, the attacker may be a boundedly rational player, who adopts a combination of the BR strategy and a fixed stubborn one. In such a condition, the SSE strategy may not maintain the defensive performance due to the stubbornness. In this paper, we focus on how the defender can adopt the unilateral-control zero-determinate (ZD) strategy to confront the boundedly rational attacker. At first, we verify the existence of ZD strategies for the defender. We then investigate the performance of the defender's ZD strategy against a boundedly rational attacker, with a comparison of the SSE strategy. Specifically, when the attacker's strategy is close to the BR strategy, the ZD strategy admits a bounded loss for the defender compared with the SSE strategy. Conversely, when the attacker's strategy is close to the stubborn strategy, the ZD strategy can bring higher defensive performance for the defender than the SSE strategy does.

High performance forward osmosis membrane with ultrathin hydrophobic nanofibrous interlayer.

The novel thin film composite (TFC) forward osmosis (FO) membrane with electrospinning nanofibers as support layer can alleviate internal concentration polarization (ICP). While the macropores of the nanofiber support layer cause defects in the polyamide (PA) layer. Therefore, hydrophobic polyvinylidene fluoride (PVDF) fine nanofibers were used as an interlayer to modulate the process of interfacial polymerization (IP) in this study. The results showed that the introduction of the interlayer improved the hydrophobicity of the support layer for achieving uniform, thin and defect-free selective polyamide (PA) layer. The water flux of TFC-PVDF was 58.26 LMH in the FO mode of 2 M NaCl, which was two times higher than that of the unmodified FO membrane. Lower reverse salt flux (4.91 gMH) and structural parameter (179.43 µm) alleviated the ICP. In addition, TFC-PVDF membrane showed good anti-fouling performance for SA (flux recovery ratio of 93.97%) due to high hydrophilicity, low zeta potential and low roughness. This study provides an easy and promising method to prepare defect-free PA selective layer on the macropores nanofiber support layer. The novel FO membrane shows high desalination performance and anti-fouling properties.

Promoting Surface Reconstruction of Low-Cost Stainless Steel Catalyst for Efficient Oxygen Evolution Reaction.

The development of cost-effective transition metal catalysts for oxygen evolution reaction (OER) is critical for the production of hydrogen fuel from water splitting. Low-cost and efficient stainless steel-based catalysts are expected to replace the scarce platinum group metals for large-scale energy applications. Here in this work, we report the conversion of commonly available inexpensive and easily accessible 434-L stainless steel (SS) into highly active and stable electrodes by corrosion and sulfuration strategies. The Nix Fe1-x S layer as a pre-catalyst and S-doped Nix Fe oxyhydroxides in situ formed on the catalyst surface are the true active species for OER. The optimized 434-L stainless steel-based electrocatalyst exhibits a low overpotential of 298 mV at 10 mA cm-2 in 1.0 M KOH with a small OER kinetics (the Tafel slope of 54.8 mV dec-1 ) and good stability. This work reveals the 434-L alloy stainless steel with Fe and Cr as the main elements can be used as qualified OER catalysts by surface modification, along with a new mentality to solve the energy and resource waste problems.

Cobalt-Catalyzed Regiodivergent Double Hydrosilylation of Arylacetylenes.

Double hydrosilylation of alkynes represents a straightforward method to synthesize bis(silane)s, yet it is challenging if α-substituted vinylsilanes act as the intermediates. Here, a cobalt-catalyzed regiodivergent double hydrosilylation of arylacetylenes is reported for the first time involving this challenge, accessing both vicinal and geminal bis(silane)s with exclusive regioselectivity. Various novel bis(silane)s containing Si-H bonds can be easily obtained. The gram-scale reactions could be performed smoothly. Preliminarily mechanistic studies demonstrated that the reactions were initiated by cobalt-catalyzed α-hydrosilylation of alkynes, followed by cobalt-catalyzed ß-hydrosilylation of the α-vinylsilanes to deliver vicinal bis(silane)s, or hydride-catalyzed α-hydrosilylation to give geminal ones. Notably, these bis(silane)s can be used for the synthesis of high-refractive-index polymers (nd up to 1.83), demonstrating great potential utility in optical materials.

UCoO4/Co3O4 Heterojunction as a Low-Cost and Efficient Electrocatalyst for Oxygen Evolution.

The development of actinide materials has provided new strategies for the utilization of nuclear waste, such as depleted uranium, a mildly radioactive waste in the nuclear power industry, which could be a precious resource for many fields, especially water splitting. The catalytic performance of water splitting is limited by the slow kinetics of the oxygen evolution reaction (OER), and it is extremely challenging to design efficient OER catalysts that are highly stable and inexpensive. Here, we design and describe a series of U5-35%-Co3O4 electrocatalysts, which were synthesized using uranyl nitrate as a precursor via a simple and scalable method. Interestingly, when the U/Co molar ratio was 20%, a UCoO4/Co3O4 heterojunction formed with high catalytic efficiency and excellent long-term electrolytic stability. The UCoO4/Co3O4 heterojunction catalyst shows a lower overpotential (280 mV) at a current density of 10 mA cm-2, and the slope of Tafel is 43.8 mV decade-1 in a 0.1 M KOH alkaline solution. Soft X-ray absorption spectroscopy shows that the cooperative effect of UCoO4 and Co3O4 can improve the electrochemical activity of the material. This study produced an active U/Co-based catalyst for OER, which provides a simple, scalable, low-cost, and highly efficient catalyst for overall water splitting.

Enhanced Hydrogen Evolution Reaction over Co Nanoparticles Embedded N-Doped Carbon Nanotubes Electrocatalyst with Zn as an Accelerant.

The rational design for transition metals-based carbon nano-materials as efficient electrocatalysts still remains a crucial challenge for economical electrochemical hydrogen production. Carbon nanotubes (CNTs) as attractive electrocatalysts are typically activated by non-metal dopant to promote catalytic performance. Metals doping or metal/non-metal co-doping of CNTs, however, are rarely explored. Herein, this work rationally designs bimetal oxide templates of ZnCo2 O4 for heterogeneously doping Zn and N into Co nanoparticles embedded carbon nanotubes (Co@Zn-N-CNTs). During the formation of CNTs, Zn atoms volatilize from ZnCo2 O4 and in situ dope into the carbon skeleton. In particular, owing to the low electronegativity of Zn, the electrons aptly transfer from Zn to carbon atoms, which generate a high electron density for the carbon layers and offer more preponderant catalytic sites for hydrogen reduction. The Co@Zn-N-CNTs catalyst exhibits enhanced hydrogen evolution reaction activity in 0.5 m H2 SO4 electrolyte, with a low onset potential of -20 mV versus RHE at 1 mA cm-2 , an overpotential of 67 mV at 10 mA cm-2 , a small Tafel slope of 52.1 mV dec-1 , and persistent long-term stability. This study provides brand-new insights into the utilization of Zn as electronic regulator and activity promoter toward the design of high-efficiency electrocatalysts.

Misperception influence on zero-determinant strategies in iterated Prisoner's Dilemma.

Zero-determinant (ZD) strategies have attracted wide attention in Iterated Prisoner's Dilemma (IPD) games, since the player equipped with ZD strategies can unilaterally enforce the two players' expected utilities subjected to a linear relation. On the other hand, uncertainties, which may be caused by misperception, occur in IPD inevitably in practical circumstances. To better understand the situation, we consider the influence of misperception on ZD strategies in IPD, where the two players, player X and player Y, have different cognitions, but player X detects the misperception and it is believed to make ZD strategies by player Y. We provide a necessary and sufficient condition for the ZD strategies in IPD with misperception, where there is also a linear relationship between players' utilities in player X's cognition. Then we explore bounds of players' expected utility deviation from a linear relationship in player X's cognition with also improving its own utility.

Desymmetrizing Isomerization of Alkene via Thiazolinyl Iminoquinoline Cobalt Catalysis.

We report a cobalt-catalyzed desymmetrizing isomerization of exo-cyclic alkenes to generate chiral 1-methylcyclohexene derivatives with good yields and enantioselectivities. A novel chiral thiazolinyl iminoquinoline ligand and its cobalt complex were designed and synthesized to control the establishment of tertiary or quaternary carbon centers at a remote position. This protocol is operationally simple, and a model for the stereochemical outcome has been proposed.

Regio-controllable Cobalt-Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes.

Regiodivergent addition reactions provide straightforward and atom-economic approaches to access different regioisomers. However, the regio-chemistry control to access all the possible results is still challenging especially for the reaction involving multiple addition steps. Herein, we reported regio-controllable cobalt-catalyzed sequential hydrosilylation/hydroboration of arylacetylenes, delivering all the possible regio-outcomes with high regioselectivities (up to >20/1 rr for all the cases). Each regioisomer of value-added silylboronates could be efficiently and regioselectively obtained from the same materials. The adjustment of the ligands of cobalt catalysts combined with dual catalysis relay strategy is the key to achieve regio-chemistry control. This regio-controllable research might inspire the exploration of the diversity-oriented synthesis that involves multiple additions and provide full sets of regioisomers of other synthetic useful molecules.

Iron- and Cobalt-Catalyzed Asymmetric Hydrofunctionalization of Alkenes and Alkynes.

Transition metal catalyzed asymmetric hydrofunctionalization of readily available unsaturated hydrocarbons presents one of the most straightforward and atom-economic protocols to access valuable optically active products. For decades, noble transition metal catalysts have laid the cornerstone in this field, on account of their superior reactivity and selectivity. In recent years, from an economical and sustainable standpoint, first-row, earth-abundant transition metals have received considerable attention, due to their high natural reserves, affordable costs, and low toxicity. Meanwhile, the earth-abundant metal catalyzed hydrofunctionalization reactions have also gained much interest and been investigated gradually. However, since chiral ligand libraries for earth-abundant transition-metal catalysis are limited to date, the development of highly enantioselective versions remains a significant challenge.This Account summarizes our recent efforts in developing suitable chiral ligands for iron and cobalt catalysts and their applications in the highly enantioselective hydrofunctionalization reactions (hydroboration and hydrosilylation) of alkenes and alkynes. In ligand design, we envisioned that chiral unsymmetric NNN-tridentate (UNT) ligand scaffolds could promote these enantioselective transformations with earth-abundant metals. Therefore, several types of chiral UNT ligands were designed and prepared in our laboratory, utilizing readily available natural amino acids as chiral sources. In the very beginning, chiral oxazoline iminopyridine (OIP) ligands were proposed and investigated through the rational combination of nitrogen-containing ligand scaffolds. After a systematic survey of the ligand effects, the imine moiety in the rigid OIP ligands was replaced by a conformationally more flexible amine unit, leading to the construction of reactive oxazoline aminoisopropylpyridine (OAP) ligands. Subsequently, imidazoline iminopyridine (IIP) and thiazoline iminopyridine (TIP) ligands were prepared by altering the oxygen atom of oxazoline with nitrogen and sulfur linkers, respectively. To further expand the chiral ligand library, other tridentate ligands containing a twisted pincer, anionic, and nonrigid backbone were also designed and synthesized, including iminophenyl oxazolinyl phenylamine (IPOPA) and imidazoline phenyl picolinamide (ImPPA). The efficacy of these chiral UNT ligands for asymmetric induction in iron and cobalt catalysis has been demonstrated through asymmetric hydrofunctionalization of alkenes and asymmetric sequential hydrofunctionalization of alkynes, which exhibit excellent reactivity as well as high chemo-, regio-, and stereoselectivity with broad functional group tolerance. Notably, highly regio- and enantioselective hydrofunctionalization of challenging substrates, such as 1,1-disubstituted aryl alkenes and terminal aliphatic alkenes, was also achieved. Furthermore, the development of asymmetric sequential isomerization/hydroboration of internal alkenes and sequential hydrofunctionalization of alkynes further demonstrates the synthetic power of these catalytic systems. The chiral enantioenriched products obtained by these methodologies could be potentially utilized in organic synthesis, medicinal chemistry, and materials science. We believe that our continuous efforts in this field would be beneficial to the development of asymmetric earth-abundant metal catalysis.

Recent advances in metal-catalysed asymmetric sequential double hydrofunctionalization of alkynes.

In recent years, metal-catalysed asymmetric sequential double hydrofunctionalization of alkynes (ASDHA) has emerged as a powerful strategy to construct valuable chiral products in an atom- and pot-economic manner utilizing readily available feedstocks. In this feature article, recent progress made in this field will be overviewed. Attention will be given to the background, substrate scopes, applications, advances and mechanistic investigations of various asymmetric sequential double hydrofunctionalizations of alkynes.

Ligand-promoted cobalt-catalyzed radical hydroamination of alkenes.

Highly regio- and enantioselective intermolecular hydroamination of alkenes is a challenging process potentially leading to valuable chiral amines. Hydroamination of alkenes via metal-catalyzed hydrogen atom transfer (HAT) with good regioselectivity and functional group tolerance has been reported, however, high enantioselectivity has not been achieved due to the lack of suitable ligands. Here we report a ligand-promoted cobalt-catalyzed Markovnikov-type selective radical hydroamination of alkenes with diazo compounds. This operationally simple protocol uses unsymmetric NNN-tridentate (UNT) ligand, readily available alkenes and hydrosilanes to construct hydrazones with good functional group tolerance. The hydrazones can undergo nitrogen-nitrogen bond cleavage smoothly to deliver valuable amine derivatives. Additionally, asymmetric intermolecular hydroamination of unactivated aliphatic terminal alkenes using chiral N-imidazolinylphenyl 8-aminoquinoline (IPAQ) ligands has also been achieved to afford chiral amine derivatives with good enantioselectivities.

Asymmetric remote C-H borylation of internal alkenes via alkene isomerization.

Recent years have witnessed the growing interest in the remote functionalization of alkenes for it offers a strategy to activate the challenging C-H bonds distant from the initiation point via alkene isomerization/functionalization. However, the catalytic enantioselective isomerization/functionalization with one single transition metal catalyst remains rare. Here we report a highly regio- and enantioselective cobalt-catalyzed remote C-H bond borylation of internal alkenes via sequential alkene isomerization/hydroboration. A chiral ligand featured twisted pincer, anionic, and non-rigid characters is designed and used for this transformation. This methodology, which is operationally simple using low catalyst loading without additional activator, shows excellent enantioselectivity and can be used to convert various internal alkenes with regio- and stereoisomers to valuable chiral secondary organoboronates with good functional group tolerance.

Iron-Catalyzed, Markovnikov-Selective Hydroboration of Styrenes.

A highly Markovnikov-selective, iron-catalyzed hydroboration of styrenes is reported using available oxazolinylphenyl picolinamide as the ligand to afford the branched hydroboration products with up to >50/1 b/l. This reaction is operationally simple and could be carried out in gram scale.