Ultrafast Room-Temperature Synthesis of Phosphate-Intercalated NiFe Layered Double Hydroxides for High-Performance Alkaline Seawater Oxidation.

Quick and easy synthetic methods and highly efficient catalytic performance are equally important to anodic oxygen evolution reaction (OER) electrocatalysts for alkaline seawater electrolysis. Herein, we report a facile one-step route to in situ growing PO43- intercalated NiFe layered double hydroxides (NiFe-LDH) on Ni foam (denoted as NiFe-P/NF) by a room-temperature immersion for several minutes. This ultrafast approach transforms the NF surface into a rough PO43- intercalated NiFe-LDH overlayer, which demonstrates outstanding OER performance in both alkaline simulated and natural seawaters owing to good hydrophilic interface and the electrostatic repulsion of PO43- against Cl- anions. Density functional theory calculations reveal that the intercalated PO43- can not only promote electron transfer but also prevent Cl- from entering the interlayer and simultaneously inhibit the migration of Cl- over the NiFe-LDH surface. In alkaline simulated and natural seawater electrolytes, NiFe-P/NF needs low overpotentials of 248 and 298 mV to achieve a current density of 100 mA cm-2, respectively. NiFe-P/NF can stably run over 42 h in an alkaline high-salty electrolyte (1 M KOH + 2.5 M NaCl) at 250 mA cm-2, more than 70 times that of NiFe/NF (0.6 h), emphasizing the critical role of the intercalated PO43- anions on the excellent durability. This study offers a new strategy to modify commercial NF to prepare efficient and stable OER catalysts for seawater electrolysis.

Ni-catalyzed enantioselective three-component reductive alkylacylation of alkenes: modular access to structurally complex α-amino ketones.

Chiral alpha-amino ketones have found extensive applications as functional molecules. A nickel-catalyzed, enantioselective, and fully intermolecular three-component 1,2-alkylacylation of N-acyl enamides has been realized with tertiary alkyl bromides and carboxylic acid-derived electrophiles as the coupling reagents. This reductive coupling strategy is operationally simple, exhibiting broad substrate scope and excellent functional group tolerance using readily available starting materials and allowing rapid access to structurally complex α-amino ketone derivatives in high enantioselectivity. A suitable chiral biimidazoline ligand together with additional chelation of the amide carbonyl group in a Ni alkyl intermediate facilitates the enantioselective control by suppressing the background reaction, accounting for the excellent enantioselectivity. Mechanistic studies indicated intermediacy of radical species.

Access to distal biaxial atropisomers by iridium catalyzed asymmetric C-H alkylation.

Distal biaxial atropisomers are typical structures in chiral catalysts and ligands and offer a wide variety of applications in biology and materials technology, but the development of efficient synthesis of these valuable scaffolds is still in great demand. Herein, we describe a highly efficient iridium catalyzed asymmetric C-H alkylation reaction that provides a range of new distal biaxial atropisomers with excellent yields (up to 99%) and stereoselectivity (up to 99% ee and essentially one isomer). Based on this unprecedented strategy, a polycyclic skeleton with five successive chiral centers as well as C-C and C-N (or N-N) two distal chiral axes was created successfully in mild circumstances. In addition, the optically pure products bearing fluorophores show circular polarized luminescence (CPL) properties, being potential candidate materials for CPL applications.

Rhodium(III)-Catalyzed Oxidative Cross-Coupling of N-Pyrimidylindoles with Cyclic ß-Keto Esters for Accessing All-Carbon Quaternary Centers.

Rh(III)-catalyzed direct oxidative C-H/C-H cross-coupling between N-pyrimidylindoles and ß-ketoesters is presented. Easily available ß-ketoesters are used as an alkylating agent for the facile construction of all-carbon quaternary centers under mild conditions. The ester group in the product can undergo decarboxylation or decarboxylative amination.

Intermolecular Buchwald-Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C-N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination.

Axially chiral biaryls featuring a C-N axis are important functional molecules in diverse fields. The asymmetric Buchwald-Hartwig reaction represents a powerful strategy for these targets. Previous studies, however, have been predominantly restricted to intramolecular atroposelective coupling, likely due to the steric and entropic effects in the reductive elimination of Pd(II) species with sterically congested aryl and nitrogen groups. We now report two intermolecular Buchwald-Hartwig coupling systems of bulky NH lactams and halohydrocarbons enabled by rerouting the mechanism of C-N reductive elimination to one that accommodates sterically challenging substrates. Both atroposelective coupling systems exhibited functional group tolerance, excellent enantioselectivity, and high Z selectivity (if applicable), affording C-N atropisomeric biaryl and olefins through de novo construction of a C-N chiral axis. Experimental and computational studies were performed to elucidate the mechanism, and the switch of the reaction pathways is traced to the steric effect (ortho substituent) of the aryl halide substrate. A bulky 2,6-disubstituted aryl halide reorients the proximal lactamide ligand to its unusual O-ligation mode. With the amide oxygen participation, this intermediate undergoes C-N reductive elimination with an accessible barrier through a five-membered ring transition state, a pathway as well as a chiral induction mode that has been much underexplored in asymmetric catalysis.

Pd-catalyzed asymmetric Larock reaction for the atroposelective synthesis of N─N chiral indoles.

Atropisomeric indoles defined by a N─N axis are an important class of heterocycles in synthetic and medicinal chemistry and material sciences. However, they remain heavily underexplored due to limited synthetic methods and challenging stereocontrol over the short N─N bonds. Here, we report highly atroposelective access to N─N axially chiral indoles via the asymmetric Larock reaction. This protocol leveraged the powerful role of chiral phosphoramidite ligand to attenuate the common ligand dissociation in the original Larock reaction, forming N─N chiral indoles with excellent functional group tolerance and high enantioselectivity via palladium-catalyzed intermolecular annulation between readily available o-iodoaniline and alkynes. The multifunctionality in the prepared chiral indoles allowed diverse post-coupling synthetic transformations, affording a broad array of functionalized chiral indoles. Experimental and computational studies have been conducted to explore the reaction mechanism, elucidating the enantio-determining and rate-limiting steps.

Boron modification promoting electrochemical surface reconstruction of NiFe-LDH for efficient and stable freshwater/seawater oxidation catalysis.

Transition metal-based electrocatalysts generally take place surface reconstruction in alkaline conditions, but little is known about how to improve the reconstruction to a highly active oxyhydroxide surface for an efficient and stable oxygen evolution reaction (OER). Herein, we develop a strategy to accelerate surface reconstruction by combining boron modification and cyclic voltammetry (CV) activation. Density functional theory calculations and in-situ/ex-situ characterizations indicate that both B-doping and electrochemical activation can reduce the energy barrier and contribute to the surface evolution into highly active oxyhydroxides. The formed oxyhydroxide active phase can tune the electronic configuration and boost the OER process. The reconstructed catalyst of CV-B-NiFe-LDH displays excellent alkaline OER performance in freshwater, simulated seawater, and natural seawater with low overpotentials at 100 mA cm-2 (η100: 219, 236, and 255 mV, respectively) and good durability. This catalyst also presents outstanding Cl- corrosion resistance in alkalized seawater electrolytes. The CV-B-NiFe-LDH||Pt/C electrolyzer reveals prominent performance for alkalized freshwater/seawater splitting. This study provides a guideline for developing advanced OER electrocatalysts by promoting surface reconstruction.

Cobalt- or rhodium-catalyzed synthesis of 1,2-dihydrophosphete oxides via C-H activation and formal phosphoryl migration.

A highly stereo- and chemoselective intermolecular coupling of diverse heterocycles with dialkynylphosphine oxides has been realized via cobalt/rhodium-catalyzed C-H bond activation. This protocol provides an efficient synthetic entry to functionalized 1,2-dihydrophosphete oxides in excellent yields via the merger of C-H bond activation and formal 1,2-migration of the phosphoryl group. Compared with traditional methods of synthesis of 1,2-dihydrophosphetes that predominantly relied on stoichiometric metal reagents, this catalytic system features high efficiency, a relatively short reaction time, atom-economy, and operational simplicity. Photophysical properties of selected 1,2-dihydrophosphete oxides are also disclosed.

Tumor-penetrating iRGD facilitates penetration of poly(floxuridine-ketal)-based nanomedicine for enhanced pancreatic cancer therapy.

Efficient intratumoral penetration is essential for nanomedicine to eradicate pancreatic tumors. Although nanomedicine can enter the perivascular space of pancreatic tumors, their access to distal tumor cells, aloof from the vessels, remains a formidable challenge. Here, we synthesized an acid-activatable macromolecular prodrug of floxuridine (FUDR)-poly(FUDR-ketal), engineered a micellar nanomedicine of FUDR, and intravenously co-administered the nanomedicine with the tumor-penetrating peptide iRGD for enhanced treatment of pancreatic tumor. A FUDR-derived mono-isopropenyl ether was synthesized and underwent self-addition polymerization to afford the hydrophobic poly(FUDR-ketal), which was subsequently co-assembled with amphiphilic DSPE-mPEG into the micellar nanomedicine with size of 12 nm and drug content of 56.8 wt% using nanoprecipitation technique. The acetone-based ketal-linked poly(FUDR-ketal) was triggered by acid to release FUDR to inhibit cell proliferation. In an orthotopic pancreatic tumor model derived from KPC (KrasLSL-G12D/+; Trp53LSL-R172H/+; Pdx1-Cre) cells that overexpress neuropilin-1 (NRP-1) receptor, iRGD improved penetration of FUDR nanomedicine into tumor parenchyma and potentiated the therapeutic efficacy. Our nanoplatform, along with iRGD, thus appears to be promising for efficient penetration and activation of acid-responsive nanomedicines for enhanced pancreatic cancer therapy.

Unraveling the crucial contribution of additive chromate to efficient and stable alkaline seawater oxidation on Ni-based layered double hydroxides.

Seawater electrolysis to generate hydrogen offers a clean, green, and sustainable solution for new energy. However, the catalytic activity and durability of anodic catalysts are plagued by the corrosion and competitive oxidation reactions of chloride in high concentrations. In this study, we find that the additive CrO42- anions in the electrolyte can not only promote the formation and stabilization of the metal oxyhydroxide active phase but also greatly mitigate the adverse effect of Cl- on the anode. Linear sweep voltammetry, accelerated corrosion experiments, corrosion polarization curves, and charge transfer resistance results indicate that the addition of CrO42- distinctly improves oxygen evolution reaction (OER) kinetics and corrosion resistance in alkaline seawater electrolytes. Especially, the introduction of CrO42- even in the highly concentrated NaCl (2.5 M) electrolyte prolongs the durability of NiFe-LDH to almost five times the case without CrO42-. Density functional theory calculations also reveal that the adsorption of CrO42- can tune the electronic configuration of active sites of metal oxyhydroxides, enhance conductivity, and optimize the intermediate adsorption energies. This anionic additive strategy can give a better enlightenment for the development of efficient and stable oxygen evolution reactions for seawater electrolysis.

What drives the green development behavior of local governments? A perspective of grounded theory.

Although the elements that lead local governments to adopt sustainable development behaviors have been examined, the underlying processes that local governments adopt to accomplish green development behavior (GDB) lack systematic theoretical analysis. This study aims to investigate the determinants influencing local governments' implementation of GDB from the organizational internal and external perspectives. This study employed grounded theory to analyze the data and develop an influencing factor model of local government green development behavior (GDB-LG) after interviewing 53 Chinese local officials. Additionally, through integrating process organization research with new institutional theory, the mechanism that explains how these elements influence GDB was investigated. The results of the study demonstrate that the influencing factors model could give municipal governments clear guidance when creating sensible green development policies, further enhancing the efficacy of GDB.

Rhodium(I)-Catalyzed Asymmetric Hydroarylative Cyclization of 1,6-Diynes to Access Atropisomerically Labile Chiral Dienes.

Axially chiral open-chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)-catalyzed hydroarylative cyclization of 1,6-diynes with three distinct classes of arenes, enabling highly enantioselective synthesis of a broad range of axially chiral 1,3-dienes that are conformationally labile (ΔG≠ (rac)=26.6-28.0 kcal/mol). The coupling reactions in each category proceeded with excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies of the coupling of quinoline N-oxide system reveal that the reaction proceeds via initial oxidative cyclization of the 1,6-diyne to give a rhodacyclic intermediate, followed by σ-bond metathesis between the arene C-H bond and the Rh-C(vinyl) bond, with subsequent C-C reductive elimination being enantio-determining and turnover-limiting. The DFT-established mechanism is consistent with the experimental studies. The coupled products of quinoline N-oxides undergo facile visible light-induced intramolecular oxygen-atom transfer, affording chiral epoxides with complete axial-to-central chirality transfer.

Rhodium-Catalyzed Enantioselective Formal [4+1] Cyclization of Benzyl Alcohols and Benzaldimines: Facile Access to Silicon-Stereogenic Heterocycles.

The carbon-to-silicon switch in formation of bioactive sila-heterocycles with a silicon-stereogenic center has garnered significant interest in drug discovery. However, metal-catalyzed synthesis of such scaffolds is still in its infancy. Herein, a rhodium-catalyzed enantioselective formal [4+1] cyclization of benzyl alcohols and benzaldimines has been realized by enantioselective difunctionalization of a secondary silane reagent, affording chiral-at-silicon cyclic silyl ethers and sila-isoindolines, respectively. Mechanistic studies reveal a dual role of the rhodium-hydride catalyst. The coupling system proceeds via rhodium-catalyzed enantio-determining dehydrogenative OH silylation of the benzyl alcohol or hydrosilylation of the imine to give an enantioenriched silyl ether or silazane intermediate, respectively. The same rhodium catalyst also enables subsequent intramolecular cyclative C-H silylation directed by the pendent Si-H group. Experimental and DFT studies have been conducted to explore the mechanism of the OH bond silylation of benzyl alcohol, where the Si-O reductive elimination from a Rh(III) hydride intermediate has been established as the enantiodetermining step.

Synthesis of Bridged Cycloisoxazoline Scaffolds via Rhodium-Catalyzed Coupling of Nitrones with Cyclic Carbonate.

Bridged isoxazolidines were synthesized via Rh(III)-catalyzed C-H allylation of α-aryl nitrones with 5-methylene-1,3-dioxan-2-one. The nitrone group serves as a directing group and 1,3-dipole in the C-H activation/[3 + 2] cycloaddition cascade, exhibiting excellent chemo- and stereoselectivity along with good functional group compatibility. The resulting skeletal structure was conveniently modified to produce a range of important chemical frameworks, and the protocol was applied to biologically active molecules.

Rhodium-Catalyzed Enantioselective Addition of Heteroarenium Salts Enabled by Nucleophilic Cyclization of 2-Alkynylanilines.

Transition-metal-catalyzed cyclative coupling of 2-alkynylanilines provides a feasible routine for accessing functionalized indoles. Herein, a rhodium-catalyzed highly enantioselective addition of heteroarenium salts is presented, which is enabled by the nucleophilic cyclization of 2-alkynylanilines. It offers feasible protocols to access enantioenriched functionalized indoles tethered to 1,2-dihydropyridine and 1,2-dihydroquinoline motifs with excellent enantioselectivities.

Explaining the Green Development Behavior of Local Governments for Sustainable Development: Evidence from China.

Although researchers have examined organizational sustainability practices, a specific interpretation of local government green development practices remains for supplemental analysis. This study conducted an empirical survey of 53 local officials from departments related to green development to understand the key processes and practices of green development behavior of local governments in China. The key findings indicate that the main stakeholders involved in the green development practices of Chinese local governments consist of enterprises and residents. In part, local government green development practices emphasize the greening of enterprises, especially in the step of process environmental regulation. The new institutionalism theory and the organizational process research provide dependable insights into green development behaviors. Our findings further shed light on the process of cross-sectoral cooperation across local government departments in green development, contributing to local multi-sectoral interactions for regional green development.

Type I Collagen-Adhesive and ROS-Scavenging Nanoreactors Enhanced Retinal Ganglion Cell Survival in an Experimental Optic Nerve Crush Model.

Traumatic optic neuropathy (TON) is a severe condition characterized by retinal ganglion cell (RGC) death, often leading to irreversible vision loss, and the death of RGCs is closely associated with oxidative stress. Unfortunately, effective treatment options for TON are lacking. To address this, catalase (CAT) is encapsulated in a tannic acid (TA)/poly(ethylenimine)-crosslinked hollow nanoreactor (CAT@PTP), which exhibited enhanced anchoring in the retina due to TA-collagen adhesion. The antioxidative activity of both CAT and TA synergistically eliminated reactive oxygen species (ROS) to save RGCs in the retina, thereby treating TON. In vitro experiments demonstrated that the nanoreactors preserve the enzymatic activity of CAT and exhibit high adhesion to type I collagen. The combination of CAT and TA-based nanoreactors enhanced ROS elimination while maintaining high biocompatibility. In an optic nerve crush rat model, CAT@PTP is effectively anchored to the retina via TA-collagen adhesion after a single vitreous injection, and RGCs are significantly preserved without adverse events. CAT@PTP exhibited a protective effect on retinal function. Given the abundance of collagen that exists in ocular tissues, these findings may contribute to the further application of this multifunctional nanoreactor in ocular diseases to improve therapeutic efficacy and reduce adverse effects.

Rh(III)-Catalyzed C-H Activation of Benzamides and Chemodivergent Annulation with Benzoxazinanones: Substrate Controlled Selectivity.

Decarboxylative annulation of propargyl carbamates with benzamides has been realized via rhodium-catalyzed C-H bond activation under mild conditions, delivering two distinct classes of heterocycles in high efficiency and selectivity under substrate control. This protocol provides a direct synthetic method for the preparation of functionalized 1,8-naphthyridines and isoindolinones.

Palladium-Catalyzed Regio- and Enantioselective Hydrophosphination of gem-Difluoroallenes.

Chiral allylic phosphines and gem-difluoroalkenes are both important structural motifs in various bioactive molecules, chiral ligands, and natural products. These two motifs are now integrated, and we herein report a straightforward and atom-economical enantioselective hydrophosphination of gem-difluoroallenes using disubstituted phosphines. A wide array of enantioenriched fluorinated allylic phosphines has been accessed with excellent regio- and enantioselectivity and high efficiency. Synthetic and catalytic applications of phosphine products have been demonstrated.

Rhodium-catalyzed annulative approach to N-N axially chiral biaryls via C-H activation and dynamic kinetic transformation.

N-N axially chiral biaryls represent a rarely explored class of atropisomeric compounds. We hereby report rhodium-catalyzed enantioselective [4 + 2] oxidative annulation of internal alkynes with benzamides bearing two classes of N-N directing groups. The coupling occurs under mild conditions via NH and CH annulation through the dynamic kinetic transformation of the directing group and is highly enantioselective with good functional tolerance. Computational studies of a coupling system at the DFT level has been conducted, and the alkyne insertion was identified as the enantio-determining as well as the turnover-limiting step.