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Achieving high energy density has always been the goal of lithium-ion batteries (LIBs). SiO x has emerged as a compelling candidate for use as a negative electrode material due to its remarkable capacity. However, the huge volume expansion and the unstable electrode interface during (de)lithiation, hinder its further development. Herein, we report a facile strategy for the synthesis of surface fluorinated SiO x (SiO x @vG-F), and investigate their influences on battery performance. Systematic experiments investigations indicate that the reaction between Li + and fluorine groups promotes the in situ formation of stable LiF-rich solid electrolyte interface (SEI) on the surface of SiO x @vG-F anode, which effectively suppresses the pulverization of microsized SiO x particles during the charge and discharge cycle. As a result, the SiO x @vG-F enabled a higher capacity retention of 86.4 % over 200 cycles at 1.0 C in the SiO x @vG-F||LiNi 0.8 Co 0.1 Mn 0.1 O 2 full cell. This approach will provide insights for the advancement of alternative electrode materials in diverse energy conversion and storage systems., (© 2024 Wiley-VCH GmbH.)

Autism spectrum disorder (ASD) is a neurodevelopmental disorder, characterized by social communication disability and stereotypic behavior. This study aims to investigate the impact of prenatal exposure to 1-nitropyrene (1-NP), a key component of motor vehicle exhaust, on autism-like behaviors in a mouse model. Three-chamber test finds that prenatal 1-NP exposure causes autism-like behaviors during the weaning period. Patch clamp shows that inhibitory synaptic transmission is reduced in medial prefrontal cortex of 1-NP-exposed weaning pups. Immunofluorescence finds that prenatal 1-NP exposure reduces the number of prefrontal glutamate decarboxylase 67 (GAD67) positive interneurons in fetuses and weaning pups. Moreover, prenatal 1-NP exposure retards tangential migration of GAD67-positive interneurons and downregulates interneuron migration-related genes, such as Nrg1, Erbb4, and Sema3F, in fetal forebrain. Mechanistically, prenatal 1-NP exposure reduces hydroxymethylation of interneuron migration-related genes through inhibiting ten-eleven translocation (TET) activity in fetal forebrain. Supplement with alpha-ketoglutarate (α-KG), a cofactor of TET enzyme, reverses 1-NP-induced hypohydroxymethylation at specific sites of interneuron migration-related genes. Moreover, α-KG supplement alleviates 1-NP-induced migration retardation of interneurons in fetal forebrain. Finally, maternal α-KG supplement improves 1-NP-induced autism-like behaviors in weaning offspring. In conclusion, prenatal 1-NP exposure causes autism-like behavior partially by altering DNA hydroxymethylation of interneuron migration-related genes in developing brain., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Large reserves, high capacity, and low cost are the core competitiveness of disordered carbon materials as excellent anode materials for sodium-ion batteries (SIBs). And the existence and improper treatment of a large number of organic solid wastes will aggravate the burden on the environment, therefore, it is significant to transform wastes into carbon-based materials for sustainable energy utilization. Herein, a kind of hard carbon materials are reported with waste biomass-foam as the precursor, which can improve the sodium storage performance through pre-oxidation strategy. The introduction of oxygen-containing groups can promote structural cross-linking, and inhibit the melting and rearrangement of carbon structure during high-temperature carbonization that produces a disordered structure with a suitable degree of graphitization. Moreover, the micropore structure are also regulated during the high-temperature carbonization process, which is conducive to the storage of sodium ions in the low-voltage plateau region. The optimized sample as an electrode material exhibits excellent reversible specific capacity (308.0 mAh g -1 ) and initial Coulombic efficiency (ICE, 90.1%). In addition, a full cell with the waste foam-derived hard carbon anode and a Na 3 V 2 (PO 4 ) 3 cathode is constructed with high ICE and energy density. This work provides an effective strategy to conversion the waste to high-value hard carbon anode for sodium-ion batteries., (© 2023 Wiley‐VCH GmbH.)

Solid-state lithium-sulfur batteries have shown prospects as safe, high-energy electrochemical storage technology for powering regional electrified transportation. Owing to limited ion mobility in crystalline polymer electrolytes, the battery is incapable of operating at subzero temperature. Addition of liquid plasticizer into the polymer electrolyte improves the Li-ion conductivity yet sacrifices the mechanical strength and interfacial stability with both electrodes. In this work, we showed that by introducing a spherical hyperbranched solid polymer plasticizer into a Li + -conductive linear polymer matrix, an integrated dynamic cross-linked polymer network was built to maintain fully amorphous in a wide temperature range down to subzero. A quasi-solid polymer electrolyte with a solid mass content >90 % was prepared from the cross-linked polymer network, and demonstrated fast Li + conduction at a low temperature, high mechanical strength, and stable interfacial chemistry. As a result, solid-state lithium-sulfur batteries employing the new electrolyte delivered high reversible capacity and long cycle life at 25 °C, 0 °C and -10 °C to serve energy storage at complex environmental conditions., (© 2023 Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

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., (© 2023 Wiley-VCH GmbH.)

The prosperity of the lithium-ion battery market is dialectically accompanied by the depletion of corresponding resources and the accumulation of spent batteries. It is an urgent priority to develop green and efficient battery recycling strategies for helping ease resources and environmental pressures at the current stage. Here, we propose a mild and efficient lithium extracting strategy based on potential controllable redox couples. Active lithium in the spent battery without discharging is extracted using a series of tailored aprotic solutions comprised of polycyclic aromatic hydrocarbons and ethers. This ensures a safe yet efficient recycling process with nearly ≈100 % lithium recovery. We further investigate the Li + -electron concerted redox reactions and the effect of solvation structure on kinetics during the extraction, and broaden the applicability of the Li-PAHs solution. This work can stimulate new inspiration for designing novel solutions to meet efficient and sustainable demands in recycling batteries., (© 2023 Wiley-VCH GmbH.)

Hard carbon anodes with all-plateau capacities below 0.1 V are prerequisites to achieve high-energy-density sodium-ion storage, which holds promise for future sustainable energy technologies. However, challenges in removing defects and improving the insertion of sodium ions head off the development of hard carbon to achieve this goal. Herein, a highly cross-linked topological graphitized carbon using biomass corn cobs through a two-step rapid thermal-annealing strategy is reported. The topological graphitized carbon constructed with long-range graphene nanoribbons and cavities/tunnels provides a multidirectional insertion of sodium ions whilst eliminating defects to absorb sodium ions at the high voltage region. Evidence from advanced techniques including in situ XRD, in situ Raman, and in situ/ex situ transmission electron microscopy (TEM) indicates that the sodium ions' insertion and Na cluster formation occurred between curved topological graphite layers and in the topological cavity of adjacent graphite band entanglements. The reported topological insertion mechanism enables outstanding battery performance with a single full low-voltage plateau capacity of 290 mAh g -1 , which is almost 97% of the total capacity., (© 2023 Wiley-VCH GmbH.)

A facile enantioselective alkynylation of cyclic ketimines attached to a neutral functional group utilizing the dual Cu(I)-CPA catalysis is described. The strategy of the alkynylation of 2-aryl-3H-indol-3-one directly to chiral propargylic amines containing indolin-3-one moiety in good yields and enantioselectivities. Moreover, gram-scale synthesis of chiral propargylamines based C2-quaternary indolin-3-ones was performed. The synthetic applications were confirmed by transformations of the products with no decrease in the yield and enantioselectivity., (© 2023 Wiley-VCH GmbH.)

The incorporation of fluorine atoms in organics improves their bioactivity and lipophilicity. Catalytic functionalization of gem-difluorodienes represents one of the most straightforward approaches to access fluorinated alkenes. In contrast to the regular 1,3-dienes that undergo diverse asymmetric di/hydrofunctionalizations, the regio- and enantioselective oxyamination of gem-difluorodienes remains untouched. Herein, we report asymmetric 1,4-oxyamination of gem-difluorodiene by chiral rhodium-catalyzed three-component coupling with readily available carboxylic acid and dioxazolone, affording gem-difluorinated 1,4-amino alcohol derivatives. Our asymmetric protocol exhibits high 1,4-regio- and enantioselectivity with utility in the late-stage modification of pharmaceuticals and natural products. Stoichiometric experiments provide evidences for the π-allylrhodium pathway. Related oxyamination was also realized when trifluoroethanol was used as an oxygen nucleophile., (© 2023 Wiley-VCH GmbH.)

A chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of 5-aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation of pyrazole-based C2-quaternary indolin-3-ones with high enantioselectivities and regioselectivities. Moreover, gram-scale synthesis of the 5-aminopyrazole-based C2-quaternary indolin-3-ones was performed, with no decrease in the yield and enantioselectivity., (© 2023 Wiley-VCH GmbH.)

Sodium-ion batteries (SIBs) have great potential for large-scale energy storage. Cellulose is an attractive material for sustainable separators, but some key issues still exist affecting its application. Herein, a cellulose-based composite separator (CP@PPC) was prepared by immersion curing of cellulose-based separators (CP) with poly(propylene carbonate) (PPC). With the assistance of PPC, the CP@PPC separator is able to operate the cell stably at high voltages (up to 4.95 V). The "pore-hopping" ion transport mechanism in CP@PPC opens up extra Na + migration paths, resulting in a high Na + transference number (0.613). The separator can also tolerate folding, bending and extreme temperature under certain circumstances. Full cells with CP@PPC reveal one-up capacity retention (96.97 %) at 2C after 500 cycles compared to cells with CP. The mechanism highlights the merits of electrolyte analogs in separator modification, making a rational design for durable devices in advanced energy storage systems., (© 2023 Wiley-VCH GmbH.)

Covalent organic frameworks (COFs) have received increased interest in recent years as an advanced class of materials. By virtue of the available monomers, multiple conformations and various linkages, COFs offer a wide range of opportunities for complex structural design and specific functional development of materials, which has facilitated the widespread application in many fields, including multi-valent metal ion batteries (MVMIBs), described as the attractive candidate replacing lithium-ion batteries (LIBs). With their robust skeletons, diverse pores, flexible structures and abundant functional groups, COFs are expected to help realize a high performance MVMIBs. In this review, we present an overview of COFs, describe advances in topology design and synthetic reactions, and study the application of COFs in MVMIBs, as well as discuss challenges and solutions in the preparation of COFs electrodes, in the hope of providing constructive insights into the future direction of COFs., (© 2022 Wiley-VCH GmbH.)

Centenarians, who show mild infections and low incidence of tumors, are the optimal model to investigate healthy aging. However, longevity related immune characteristics has not been fully revealed largely due to lack of appropriate controls. In this study, single-cell transcriptomic analysis of peripheral blood mononuclear cells (PBMCs) derived from seven centenarians (CEN), six centenarians' offspring (CO), and nine offspring spouses or neighbors (Control, age-matched to CO) are performed to investigate the shared immune features between CEN and CO. The results indicate that among all 12 T cell clusters, the cytotoxic-phenotype-clusters (CPC) and the naïve-phenotype-clusters (NPC) significantly change between CEN and ontrol. Compared to Control, both CEN and CO are characterized by depleted NPC and increased CPC, which is dominated by CD8 + T cells. Furthermore, CPC from CEN and CO share enhanced signaling pathways and transcriptional factors associated with immune response, and possesse similar T-cell-receptor features, such as high clonal expansion. Interestingly, rather than a significant increase in GZMK + CD8 cells during aging, centenarians show accumulation of GZMB + and CMC1 + CD8 T cells. Collectively, this study unveils an immune remodeling pattern reflected by both quantitative increase and functional reinforcement of cytotoxic T cells which are essential for healthy aging., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Both Alzheimer's disease (AD) and osteoporosis (OP) are common age-associated degenerative diseases and are strongly correlated with clinical epidemiology. However, there is a lack of clear pathological relationship between the brain and bone in the current understanding. Here, it is found that young osteocyte, the most abundant cells in bone, secretes extracellular vesicles (OCY Young -EVs) to ameliorate cognitive impairment and the pathogenesis of AD in APP/PS1 mice and model cells. These benefits of OCY Young -EVs are diminished in aged osteocyte-derived EVs (OCY Aged -EVs). Based on the self-constructed OCY-EVs tracer transgenic mouse models and the in vivo fluorescent imaging system, OCY-EVs have been observed to be transported to the brain under physiological and pathological conditions. In the hippocampal administration of Aβ40 induced young AD model mice, the intramedullary injection of Rab27a-shRNA adenovirus inhibits OCY Young -EVs secretion from bone and aggravates cognitive impairment. Proteomic quantitative analysis reveals that OCY Young -EVs, compared to OCY Aged -EVs, enrich multiple protective factors of AD pathway. The study uncovers the role of OCY-EV as a regulator of brain health, suggesting a novel mechanism in bone-brain communication., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Covalent organic frameworks (COF) possess a robust and porous crystalline structure, making them an appealing candidate for energy storage. Herein, we report an exfoliated polyimide COF composite (P-COF@SWCNT) prepared by an in situ condensation of anhydride and amine on the single-walled carbon nanotubes as advanced anode for potassium-ion batteries (PIBs). Numerous active sites exposed on the exfoliated frameworks and the various open pathways promote the highly efficient ion diffusion in the P-COF@SWCNT while preventing irreversible dissolution in the electrolyte. During the charging/discharging process, K + is engaged in the carbonyls of imide group and naphthalene rings through the enolization and π-K + effect, which is demonstrated by the DFT calculation and XPS, ex-situ FTIR, Raman. As a result, the prepared P-COF@SWCNT anode enables an incredibly high reversible specific capacity of 438 mA h g -1 at 0.05 A g -1 and extended stability. The structural advantage of P-COF@SWCNT enables more insights into the design and versatility of COF as an electrode., (© 2022 Wiley-VCH GmbH.)

The safety of energy storage equipment has always been a stumbling block to the development of battery, and sodium ion battery is no exception. However, as an ultimate solution, the use of non-flammable electrolyte is susceptible to the side effects, and its poor compatibility with electrode, causing failure of batteries. Here, we report a non-flammable electrolyte design to achieve high-performance sodium ion battery, which resolves the dilemma via regulating the solvation structure of electrolyte by hydrogen bonds and optimizing the electrode-electrolyte interphase. The reported non-flammable electrolyte allows stable charge-discharge cycling of both sodium vanadium phosphate@hard carbon and Prussian blue@hard carbon full pouch cell for more than 120 cycles with a capacity retention of >85 % and high cycling Coulombic efficiency (99.7 %)., (© 2021 Wiley-VCH GmbH.)

High-valent iron-imido complexes can perform C-H activation and sulfimidation reactions, but are far less studied than the more ubiquitous iron-oxo species. As case studies, we have looked at a recently published iron(V)-imido ligand π-cation radical complex, which is formally an iron(VI)-imido complex [Fe V (NTs)(TAML +. )] (1; NTs=tosylimido), and an iron(V)-imido complex [Fe V (NTs)(TAML)] - (2). Using a theoretical approach, we found that they have multiple energetically close-lying electromers, sometimes even without changing spin states, reminiscent of the so-called Compound I in Cytochrome P450. When studying their reactivity theoretically, it is indeed found that their electronic structures may change to perform efficient oxidations, emulating the multi-spin state reactivity in Fe IV O systems. This is actually in contrast to the known [Fe V (O)(TAML)] - species (3), where the reactions occur only on the ground spin state. We also looked into the whole reaction pathway for the C-H bond activation of 1,4-cyclohexadiene by these intermediates to reproduce the experimentally observed products, including steps that usually attract no interest (neither theoretically nor experimentally) due to their non-rate-limiting status and fast reactivity. A new "clustering non-rebound mechanism" is presented for this C-H activation reaction., (© 2021 Wiley-VCH GmbH.)

A differentiation switch of bone marrow mesenchymal stem/stromal cells (BMSCs) from osteoblasts to adipocytes contributes to age- and menopause-associated bone loss and marrow adiposity. Here it is found that osteocytes, the most abundant bone cells, promote adipogenesis and inhibit osteogenesis of BMSCs by secreting neuropeptide Y (NPY), whose expression increases with aging and osteoporosis. Deletion of NPY in osteocytes generates a high bone mass phenotype, and attenuates aging- and ovariectomy (OVX)-induced bone-fat imbalance in mice. Osteocyte NPY production is under the control of autonomic nervous system (ANS) and osteocyte NPY deletion blocks the ANS-induced regulation of BMSC fate and bone-fat balance. γ-Oryzanol, a clinically used ANS regulator, significantly increases bone formation and reverses aging- and OVX-induced osteocyte NPY overproduction and marrow adiposity in control mice, but not in mice lacking osteocyte NPY. The study suggests a new mode of neuronal control of bone metabolism through the ANS-induced regulation of osteocyte NPY., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Intercalation-based anode materials can be considered as the most promising anode candidates for large-scale sodium-ion batteries (SIBs), owing to their long-term cycling stability and environmental friendliness, as well as their natural abundance. Nevertheless, their low energy density, low initial coulombic efficiency, and poor cycling lifespan, as well as sluggish sodium diffusion dynamics are still the main issues for the application of intercalation-based anode materials in SIBs in terms of meeting the benchmark requirements for commercialization. Over the past few years, tremendous efforts have been devoted to improving the performance of SIBs. In this Review, recent progress in the development of intercalation-based anode materials, including TiO 2 , Li 4 Ti 5 O 12 , Na 2 Ti 3 O 7 , and NaTi 2 (PO 4 ) 3 , is summarized in terms of their sodium storage performance, critical issues, sodiation/desodiation behavior, and effective strategies to enhance their electrochemical performance. Additionally, challenges and perspectives are provided to further understand these intercalation-based anode materials., (© 2021 Wiley-VCH GmbH.)

As the power supply of the prosperous new energy products, advanced lithium ion batteries (LIBs) are widely applied to portable energy equipment and large-scale energy storage systems. To broaden the applicable range, considerable endeavours have been devoted towards improving the energy and power density of LIBs. However, the side reaction caused by the close contact between the electrode (particularly the cathode) and the electrolyte leads to capacity decay and structural degradation, which is a tricky problem to be solved. In order to overcome this obstacle, the researchers focused their attention on electrolyte additives. By adding additives to the electrolyte, the construction of a stable cathode-electrolyte interphase (CEI) between the cathode and the electrolyte has been proven to competently elevate the overall electrochemical performance of LIBs. However, how to choose electrolyte additives that match different cathode systems ideally to achieve stable CEI layer construction and high-performance LIBs is still in the stage of repeated experiments and exploration. This article specifically introduces the working mechanism of diverse electrolyte additives for forming a stable CEI layer and summarizes the latest research progress in the application of electrolyte additives for LIBs with diverse cathode materials. Finally, we tentatively set forth recommendations on the screening and customization of ideal additives required for the construction of robust CEI layer in LIBs. We believe this minireview will have a certain reference value for the design and construction of stable CEI layer to realize desirable performance of LIBs., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Smart devices, nowadays, are inspiring the infinite vitality and possibilities of intelligent life, such as self-power electromagnetic (EM) nanogenerator and microsensor, smart window, thermally-driven EM absorber, interstellar energy deliverer, and so on. Herein, the latest and most impressive works of 3D nano-micro architectures and their smart EM devices are highly focused on. The most key information, including assembly strategy and mechanism, EM response, and approach-structure-function relationship, is extracted and well-organized with profundity and easy-to-understand approach. The merit and demerit are revealed by comparison. What's more, the brightest and most cutting-edge smart EM devices constructed by 3D nano-micro architectures are reported as highlights, and the device principles are deeply dissected. Finally, a profound and top comment on the fast-growing field as well as challenges are proposed, and the future directions are predicted intelligently., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Humans are undergoing a fateful transformation focusing on artificial intelligence, quantum information technology, virtual reality, etc., which is inseparable from intelligent nano-micro devices. However, the booming of "Big Data" brings about an even greater challenge by growing electromagnetic radiation. Herein, an innovative flexible multifunctional microsensor is proposed, opening up a new horizon for intelligent devices. It integrates "non-crosstalk" multiple perception and green electromagnetic interference shielding only in one pixel, with satisfactory sensitivity and fast information feedback. Importantly, beneficial by deep insight into the variable-temperature electromagnetic response, the microsensor tactfully transforms the urgent threat of electromagnetic radiation into "wealth," further integrating self-power. This result will refresh researchers' realization of next-generation devices, ushering in a new direction for aerospace engineering, remote sensing, communications, medical treatment, biomimetic robot, prosthetics, etc., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Scope: The intake of resistant starch (RS) may attenuate the risks of chronic illness, including colorectal cancer. However, whether the attenuated functionality of RS is maintained in cooked meat products needs to be clarified., Methods and Results: The effects of a cooked mixture of lean pork meat and RS (MS) on the growth performance, lipid accumulation, and intestinal health of mice is investigated compared to those of RS-free cooked meat (M) and the addition of RS to cooked meat (M+S). The results show that both M+S and MS diets improve growth performance, alleviate lipid accumulation, and ameliorate colon health via promoting food intake and body weight gain, attenuating adipose tissue weight and triglyceride levels in liver and serum, regulating short-chain fatty acids and ammonia concentrations, ameliorating gut morphology and remodeling the gut microbiome, including Desulfovibrio, Escherichia-Shigella, Lactococcus, Ruminococcus 2, and the Firmicutes-to-Bacteroidetes ratio in mice, compared to the M diet. In particular, the MS diet exerts preferable effects on promoting growth performance and intestinal benefits and alleviating lipid accumulation in mice., Conclusion: Cooked mixtures of meat and RS are promising for developing novel functional meat products for nutritional health interventions., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A mononuclear manganese(V)-oxo complex with tetraamido macrocyclic ligand (TAML), [Mn V (O)(TAML)] - (1), is a sluggish oxidant in oxidation reactions. Herein, a mononuclear manganese(V)-oxo TAML cation radical complex, [Mn V (O)(TAML +. )] (2), is reported. It was synthesized by reacting [Mn III (TAML)] - with 3.0 equivalents of [Ru III (bpy) 3 ] 3+ or upon addition of one-electron oxidant to 1 and then characterized thoroughly with various spectroscopic techniques along with DFT calculations. Although 1 is a sluggish oxidant, 2 is a strong oxidant capable of activating C-H bonds of hydrocarbons (i.e., hydrogen atom transfer reaction) and transferring its oxygen atom to thioanisoles and olefins (i.e., oxygen atom transfer reaction)., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Oxygen activation plays a crucial role in many important chemical reactions such as oxidation of organic compounds and oxygen reduction. For developing highly active materials for oxygen activation, herein, we report an atomically dispersed Pt on WO 3 nanoplates stabilized by in situ formed amorphous H 2 WO 4 out-layer and the mechanism for activating molecular oxygen. Experimental and theoretical studies demonstrate that the isolated Pt atoms coordinated with oxygen atoms from [WO 6 ] and water of H 2 WO 4 , consequently leading to optimized surface electronic configuration and strong metal-support interaction (SMSI). In exemplified reactions of butanone oxidation sensing and oxygen reduction, the atomic Pt/WO 3 hybrid exhibits superior activity than those of Pt nanoclusters/WO 3 and bare WO 3 as well as enhanced long-term durability. This work will provide insight into the origin of activity and stability for atomically dispersed materials, thus promoting the development of highly efficient and durable single atom-based catalysts., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Observation of visible light trapping in zinc oxide (ZnO) nanorods (NRs) correlated to the optical and photoelectrochemical properties is reported. In this study, ZnO NR diameter and c-axis length respond primarily at two different regions, UV and visible light, respectively. ZnO NR diameter exhibits UV absorption where large ZnO NR diameter area increases light absorption ability leading to high efficient electron-hole pair separation. On the other hand, ZnO NR c-axis length has a dominant effect in visible light resulting from a multiphoton absorption mechanism due to light reflection and trapping behavior in the free space between adjacent ZnO NRs. Furthermore, oxygen vacancies and defects in ZnO NRs are associated with the broad visible emission band of different energy levels also highlighting the possibility of the multiphoton absorption mechanism. It is demonstrated that the minimum average of ZnO NR c-axis length must satisfy the linear regression model of Z p,min = 6.31d to initiate the multiphoton absorption mechanism under visible light. This work indicates the broadening of absorption spectrum from UV to visible light region by incorporating a controllable diameter and c-axis length on vertically aligned ZnO NRs, which is important in optimizing the design and functionality of electronic devices based on light absorption mechanism., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Three new proton conductors with simple structures based on isolated olyoxometalate anions as well as protonated imidazole and benzimidazole, namely, NNU-6-8, have been successfully prepared by hydrothermal reaction. We could control the number of proton sources by selecting different types and changing the charges of POM anions. The single crystal sample of NNU-6 along a-axis shows a highest proton conductivity of 1.91×10 -2  S cm -1 , which is two and three orders of magnitude higher than that of 2.42×10 -4 and 8.90×10 -5  S cm -1 along b- and c-axes, respectively, due to the more unobstructed H-bonding network and stronger π-π stacking between benzimidazole rings as proton-transferring pathway along a-axis than that along b and c axes. It is a straightforward model to understand the metaphysical proton-conducting process, and this is the first time to put forward the idea that π-π stacking could assist proton transfer and be in favor of proton conduction, which has been demonstrated by calculating potential energy surfaces of proton transfer between benzimidazole molecules., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficiently. In this work, we present results of a computational study on the reactivity patterns of Compound I, Compound II, and protonated Compound II with model substrates, and we address the question of which of these compounds is the most effective oxidant? All calculations, regardless of the substrate, implicated that Compound I is the superior oxidant of the three. However, Compound II and protonated Compound II were found to react with free energies of activation that are only a few kcal mol -1 higher in energy than those obtained with Compound I. Therefore, Compound II and protonated Compound II should be able to react with aliphatic groups with moderate C-H bond strengths. We have analysed all results in detail and have given electronic, thermochemical, valence bond, and molecular orbital rationalizations on the reactivity differences and explained experimental product distributions. Overall, the findings implied that alternative oxidants could operate alongside Compound I in complex reaction mechanisms of enzymatic and synthetic iron porphyrinoid complexes., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Surface functionalization is an essential pre requisite for wide and specific applications of nanoparticles such as photoluminescent (PL) carbon quantum dots (CQDs), but it remains a major challenge. In this report, alkynylated CQDs, prepared from carboxyl-rich CQDs through amidation with propargylamine in the presence of 1,1'-carbonyldiimidazole, were modified efficiently with azido molecular beacon DNA through a copper(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC). As a proof-of-concept, the DNA-modified CQDs are then bonded with gold nanoparticles (AuNPs, 5 nm) through a gold-sulfur bond. Owing to the emission enhancement, this complex can then be applied to the recognition of a single-base- mismatched target. The same functionalizing strategy applied to click the alkynylated CQDs with a nuclear localization sequence (NLS) peptide showed that the NLS-modified CQDs could target the nuclei specifically. These results indicate that surface functionalization of CQDs through a nonstoichiometric copper chalcogenide nanocrystal- (nsCuCNC-) catalyzed click reaction is efficient, and has significant potential in the fields of biosensing and bioimaging., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

By introducing 2,6-bis(2-benzimidazolyl)pyridyl and 2,6-di-(pyrazol-3-yl)pyridine derivatives as ligand in the reaction system, three new transition-metal coordination complexes have been successfully synthesized, namely, [Co(HL 1 ) 2 ] (1), [Ni(HL 1 ) 2 ] (2), and [Ni 3 (H 2 L 2 ) 2 ⋅(HL 2 ) 2 ]⋅(OH) 3 ⋅(Ac)⋅H 2 O (3) (H 2 L 1 =2,6-bis(benzimidazol-2-yl)pyridine and H 2 L 2 =2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine). They are all characterized by elemental analysis, IR spectroscopy, UV absorption spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analysis shows that the structures of complexes 1 and 2 are similar. They are constructed from one metal (Co, Ni) atom and two 2,6-bis(benzimidazol-2-yl)pyridine ligands (HL 1 - ); the HL 1 - ligand is in the tridentate coordination mode with N3 donors. Complex 3 is a trinuclear Ni complex with four 2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine (H 2 L 2 ) ligands, in which the H 2 L 2 possesses two coordination fashions: terminal tridentate and bridging tetradentate. In addition, the surface photovoltage spectroscopy and photocatalytic activities of complexes 1-3 were investigated in detail. The results reveal that complex 3 possesses higher photocatalytic activity., (Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first catalytic asymmetric construction of a spirooxindole scaffold incorporated with a seven-membered benzodiazepine moiety has been established by a three-component (isatin, 1,2-phenylenediamine, cyclohexane-1,3-dione) tandem reaction catalyzed by a chiral phosphoric acid. Structurally complex spirobenzodiazepine oxindoles with one quaternary stereogenic center are obtained in high yield with excellent enantioselectivity (up to 99% yield, enantiomeric ratio>99.5:0.5). This approach takes advantage of organocatalytic asymmetric tandem reactions to efficiently construct the structurally rigid spirobenzodiazepine oxindole architecture with high enantiopurity in a single transformation, which involves a cascade enamine-imine formation/intramolecular Mannich reaction sequence., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)