Showing papers by "Nankai University published in 2016"
TL;DR: In this paper, the authors present a set of guidelines for the selection and interpretation of methods for use by investigators who aim to examine macro-autophagy and related processes, as well as for reviewers who need to provide realistic and reasonable critiques of papers that are focused on these processes.
Abstract: In 2008 we published the first set of guidelines for standardizing research in autophagy. Since then, research on this topic has continued to accelerate, and many new scientists have entered the field. Our knowledge base and relevant new technologies have also been expanding. Accordingly, it is important to update these guidelines for monitoring autophagy in different organisms. Various reviews have described the range of assays that have been used for this purpose. Nevertheless, there continues to be confusion regarding acceptable methods to measure autophagy, especially in multicellular eukaryotes.
For example, a key point that needs to be emphasized is that there is a difference between measurements that monitor the numbers or volume of autophagic elements (e.g., autophagosomes or autolysosomes) at any stage of the autophagic process versus those that measure flux through the autophagy pathway (i.e., the complete process including the amount and rate of cargo sequestered and degraded). In particular, a block in macroautophagy that results in autophagosome accumulation must be differentiated from stimuli that increase autophagic activity, defined as increased autophagy induction coupled with increased delivery to, and degradation within, lysosomes (in most higher eukaryotes and some protists such as Dictyostelium) or the vacuole (in plants and fungi). In other words, it is especially important that investigators new to the field understand that the appearance of more autophagosomes does not necessarily equate with more autophagy. In fact, in many cases, autophagosomes accumulate because of a block in trafficking to lysosomes without a concomitant change in autophagosome biogenesis, whereas an increase in autolysosomes may reflect a reduction in degradative activity. It is worth emphasizing here that lysosomal digestion is a stage of autophagy and evaluating its competence is a crucial part of the evaluation of autophagic flux, or complete autophagy.
Here, we present a set of guidelines for the selection and interpretation of methods for use by investigators who aim to examine macroautophagy and related processes, as well as for reviewers who need to provide realistic and reasonable critiques of papers that are focused on these processes. These guidelines are not meant to be a formulaic set of rules, because the appropriate assays depend in part on the question being asked and the system being used. In addition, we emphasize that no individual assay is guaranteed to be the most appropriate one in every situation, and we strongly recommend the use of multiple assays to monitor autophagy. Along these lines, because of the potential for pleiotropic effects due to blocking autophagy through genetic manipulation, it is imperative to target by gene knockout or RNA interference more than one autophagy-related protein. In addition, some individual Atg proteins, or groups of proteins, are involved in other cellular pathways implying that not all Atg proteins can be used as a specific marker for an autophagic process. In these guidelines, we consider these various methods of assessing autophagy and what information can, or cannot, be obtained from them. Finally, by discussing the merits and limits of particular assays, we hope to encourage technical innovation in the field.
5,187 citations
TL;DR: A framework for adaptive visual object tracking based on structured output prediction that is able to outperform state-of-the-art trackers on various benchmark videos and can easily incorporate additional features and kernels into the framework, which results in increased tracking performance.
Abstract: Adaptive tracking-by-detection methods are widely used in computer vision for tracking arbitrary objects. Current approaches treat the tracking problem as a classification task and use online learning techniques to update the object model. However, for these updates to happen one needs to convert the estimated object position into a set of labelled training examples, and it is not clear how best to perform this intermediate step. Furthermore, the objective for the classifier (label prediction) is not explicitly coupled to the objective for the tracker (estimation of object position). In this paper, we present a framework for adaptive visual object tracking based on structured output prediction. By explicitly allowing the output space to express the needs of the tracker, we avoid the need for an intermediate classification step. Our method uses a kernelised structured output support vector machine (SVM), which is learned online to provide adaptive tracking. To allow our tracker to run at high frame rates, we (a) introduce a budgeting mechanism that prevents the unbounded growth in the number of support vectors that would otherwise occur during tracking, and (b) show how to implement tracking on the GPU. Experimentally, we show that our algorithm is able to outperform state-of-the-art trackers on various benchmark videos. Additionally, we show that we can easily incorporate additional features and kernels into our framework, which results in increased tracking performance.
1,507 citations
TL;DR: A remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis.
Abstract: Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMn2O4/carbon composite as a new Zn-insertion cathode material in aqueous Zn(CF3SO3)2 electrolyte. In 3 M Zn(CF3SO3)2 solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g–1 and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g–1. The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and pr...
1,337 citations
TL;DR: Recent progress in the applications of hierarchically structured porous materials from energy conversion and storage, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine is reviewed and could stimulate researchers to synthesize new advanced hierarchically porous solids.
Abstract: Over the last decade, significant effort has been devoted to the applications of hierarchically structured porous materials owing to their outstanding properties such as high surface area, excellent accessibility to active sites, and enhanced mass transport and diffusion. The hierarchy of porosity, structural, morphological and component levels in these materials is key for their high performance in all kinds of applications. The introduction of hierarchical porosity into materials has led to a significant improvement in the performance of materials. Herein, recent progress in the applications of hierarchically structured porous materials from energy conversion and storage, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine is reviewed. Their potential future applications are also highlighted. We particularly dwell on the relationship between hierarchically porous structures and properties, with examples of each type of hierarchically structured porous material according to its chemical composition and physical characteristics. The present review aims to open up a new avenue to guide the readers to quickly obtain in-depth knowledge of applications of hierarchically porous materials and to have a good idea about selecting and designing suitable hierarchically porous materials for a specific application. In addition to focusing on the applications of hierarchically porous materials, this comprehensive review could stimulate researchers to synthesize new advanced hierarchically porous solids.
1,052 citations
TL;DR: This Review covers the major advances with the most general applicability and emphasizes new insights into the development of efficient platform methodologies for building reliable molecular electronic devices with desired functionalities through the combination of programmed bottom-up self-assembly and sophisticated top-down device fabrication.
Abstract: Creating functional electrical circuits using individual or ensemble molecules, often termed as “molecular-scale electronics”, not only meets the increasing technical demands of the miniaturization of traditional Si-based electronic devices, but also provides an ideal window of exploring the intrinsic properties of materials at the molecular level. This Review covers the major advances with the most general applicability and emphasizes new insights into the development of efficient platform methodologies for building reliable molecular electronic devices with desired functionalities through the combination of programmed bottom-up self-assembly and sophisticated top-down device fabrication. First, we summarize a number of different approaches of forming molecular-scale junctions and discuss various experimental techniques for examining these nanoscale circuits in details. We then give a full introduction of characterization techniques and theoretical simulations for molecular electronics. Third, we highlig...
949 citations
TL;DR: The Jiangmen Underground Neutrino Observatory (JUNO) as mentioned in this paper is a 20kton multi-purpose underground liquid scintillator detector with the determination of neutrino mass hierarchy (MH) as a primary physics goal.
Abstract: The Jiangmen Underground Neutrino Observatory (JUNO), a 20 kton multi-purpose underground liquid scintillator detector, was proposed with the determination of the neutrino mass hierarchy (MH) as a primary physics goal. The excellent energy resolution and the large fiducial volume anticipated for the JUNO detector offer exciting opportunities for addressing many important topics in neutrino and astro-particle physics. In this document, we present the physics motivations and the anticipated performance of the JUNO detector for various proposed measurements. Following an introduction summarizing the current status and open issues in neutrino physics, we discuss how the detection of antineutrinos generated by a cluster of nuclear power plants allows the determination of the neutrino MH at a 3–4σ significance with six years of running of JUNO. The measurement of antineutrino spectrum with excellent energy resolution will also lead to the precise determination of the neutrino oscillation parameters ${\mathrm{sin}}^{2}{\theta }_{12}$, ${\rm{\Delta }}{m}_{21}^{2}$, and $| {\rm{\Delta }}{m}_{{ee}}^{2}| $ to an accuracy of better than 1%, which will play a crucial role in the future unitarity test of the MNSP matrix. The JUNO detector is capable of observing not only antineutrinos from the power plants, but also neutrinos/antineutrinos from terrestrial and extra-terrestrial sources, including supernova burst neutrinos, diffuse supernova neutrino background, geoneutrinos, atmospheric neutrinos, and solar neutrinos. As a result of JUNO's large size, excellent energy resolution, and vertex reconstruction capability, interesting new data on these topics can be collected. For example, a neutrino burst from a typical core-collapse supernova at a distance of 10 kpc would lead to ∼5000 inverse-beta-decay events and ∼2000 all-flavor neutrino–proton ES events in JUNO, which are of crucial importance for understanding the mechanism of supernova explosion and for exploring novel phenomena such as collective neutrino oscillations. Detection of neutrinos from all past core-collapse supernova explosions in the visible universe with JUNO would further provide valuable information on the cosmic star-formation rate and the average core-collapse neutrino energy spectrum. Antineutrinos originating from the radioactive decay of uranium and thorium in the Earth can be detected in JUNO with a rate of ∼400 events per year, significantly improving the statistics of existing geoneutrino event samples. Atmospheric neutrino events collected in JUNO can provide independent inputs for determining the MH and the octant of the ${\theta }_{23}$ mixing angle. Detection of the (7)Be and (8)B solar neutrino events at JUNO would shed new light on the solar metallicity problem and examine the transition region between the vacuum and matter dominated neutrino oscillations. Regarding light sterile neutrino topics, sterile neutrinos with ${10}^{-5}\,{{\rm{eV}}}^{2}\lt {\rm{\Delta }}{m}_{41}^{2}\lt {10}^{-2}\,{{\rm{eV}}}^{2}$ and a sufficiently large mixing angle ${\theta }_{14}$ could be identified through a precise measurement of the reactor antineutrino energy spectrum. Meanwhile, JUNO can also provide us excellent opportunities to test the eV-scale sterile neutrino hypothesis, using either the radioactive neutrino sources or a cyclotron-produced neutrino beam. The JUNO detector is also sensitive to several other beyondthe-standard-model physics. Examples include the search for proton decay via the $p\to {K}^{+}+\bar{
u }$ decay channel, search for neutrinos resulting from dark-matter annihilation in the Sun, search for violation of Lorentz invariance via the sidereal modulation of the reactor neutrino event rate, and search for the effects of non-standard interactions. The proposed construction of the JUNO detector will provide a unique facility to address many outstanding crucial questions in particle and astrophysics in a timely and cost-effective fashion. It holds the great potential for further advancing our quest to understanding the fundamental properties of neutrinos, one of the building blocks of our Universe.
807 citations
13 Apr 2016
TL;DR: This paper proposes a deep learning approach for accelerating magnetic resonance imaging (MRI) using a large number of existing high quality MR images as the training datasets and an off-line convolutional neural network to identify the mapping relationship between the MR images obtained from zero-filled and fully-sampled k-space data.
Abstract: This paper proposes a deep learning approach for accelerating magnetic resonance imaging (MRI) using a large number of existing high quality MR images as the training datasets. An off-line convolutional neural network is designed and trained to identify the mapping relationship between the MR images obtained from zero-filled and fully-sampled k-space data. The network is not only capable of restoring fine structures and details but is also compatible with online constrained reconstruction methods. Experimental results on real MR data have shown encouraging performance of the proposed method for efficient and accurate imaging.
728 citations
TL;DR: A novel approach for fabricating a series of TMPs by pyrolyzing phytic acid (PA) cross-linked metal complexes is described, demonstrating its potential for practical overall water splitting without the use of noble metals.
Abstract: Application of transition metal phosphide (TMP) catalysts for full water splitting has great potential to help relieve the energy crisis. Various methods have been investigated to obtain high catalytic activity, but the use of electronic structure regulation by incorporation of different elements is of particular simplicity and significance for development of a universal TMP synthesis method. We herein describe a novel approach for fabricating a series of TMPs by pyrolyzing phytic acid (PA) cross-linked metal complexes. The introduction of oxygen atoms into TMPs not only enhanced their intrinsic electrical conductivity, facilitating electron transfer, but activated active sites via elongating the M–P bond, favoring the hydrogen evolution reaction (HER) or oxygen evolution reaction (OER). MoP exhibited relative low HER overpotentials of 118 mV and 93 mV while supporting a current density of 20 mA·cm–2 in 0.5 M H2SO4 and 1 M KOH electrolytes, respectively. When CoP was applied as a catalyst for OER, only 28...
601 citations
TL;DR: Tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets shows that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts.
Abstract: Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts.
516 citations
TL;DR: The advances in the construction of all-carbon quaternary stereocenters via catalytic enantioselective desymmetrization of prochiral and meso-compounds are summarized and synthetic opportunities still available are outlined.
Abstract: This Review summarizes the advances in the construction of all-carbon quaternary stereocenters via catalytic enantioselective desymmetrization of prochiral and meso-compounds, highlights the power and potential of this strategy in the total synthesis of natural products and biologically active compounds, and outlines the synthetic opportunities still available.
492 citations
TL;DR: Ionic liquids and their solid-state analogues, organic ionic plastic crystals, have recently emerged as important materials for renewable energy applications as discussed by the authors, and their application as electrolytes for batteries, capacitors, photovoltaics, fuel cells and CO2 reduction.
Abstract: Ionic liquids and their solid-state analogues, organic ionic plastic crystals, have recently emerged as important materials for renewable energy applications. This Review highlights recent advances in the synthesis of these materials and their application as electrolytes for batteries, capacitors, photovoltaics, fuel cells and CO2 reduction.
TL;DR: In this article, an Urchin-like CoSe2 assembled by nanorods has been synthesized via simple solvothermal route and has been first applied as an anode material for sodium-ion batteries with ether-based electrolytes.
Abstract: Urchin-like CoSe2 assembled by nanorods has been synthesized via simple solvothermal route and has been first applied as an anode material for sodium-ion batteries (SIBs) with ether-based electrolytes. The CoSe2 delivers excellent sodiation and desodiation properties when using 1 m NaCF3SO3 in diethyleneglycol dimethylether as an electrolyte and cycling between 0.5 and 3.0 V. A high discharge capacity of 0.410 Ah g−1 is obtained at 1 A g−1 after 1800 cycles, corresponding to a capacity retention of 98.6% calculated from the 30th cycle. Even at an ultrahigh rate of 50 A g−1, the capacity still maintains 0.097 Ah g−1. The reaction mechanism of the as-prepared CoSe2 is also investigated. The results demonstrate that at discharged 1.56 V, insertion reaction occurs, while two conversion reactions take place at the second and third plateaus around 0.98 and 0.65 V. During the charge process, Co first reacts with Na2Se to form NaxCoSe2 and then turns back to CoSe2. In addition to Na/CoSe2 half cells, Na3V2(PO4)3/CoSe2 full cell with excessive amount of Na3V2(PO4)3 has been studied. The full cell exhibits a reversible capacity of 0.380 Ah g−1. This work definitely enriches the possibilities for anode materials for SIBs with high performance.
TL;DR: The progress made so far will guide further developments in the structural design of nanocarbon-based electrode materials and the configurational diversity of supercapacitor devices.
Abstract: As energy storage devices, supercapacitors that are also called electrochemical capacitors possess high power density, excellent reversibility and long cycle life. The recent boom in electronic devices with different functions in transparent LED displays, stretchable electronic systems and artificial skin has increased the demand for supercapacitors to move towards light, thin, integrated macro- and micro-devices with transparent, flexible, stretchable, compressible and/or wearable abilities. The successful fabrication of such supercapacitors depends mainly on the preparation of innovative electrode materials and the design of unconventional supercapacitor configurations. Tremendous research efforts have been recently made to design and construct innovative nanocarbon-based electrode materials and supercapacitors with unconventional configurations. We review here recent developments in supercapacitors from nanocarbon-based electrode materials to device configurations. The advances in nanocarbon-based electrode materials mainly include the assembly technologies of macroscopic nanostructured electrodes with different dimensions of carbon nanotubes/nanofibers, graphene, mesoporous carbon, activated carbon, and their composites. The electrodes with macroscopic nanostructured carbon-based materials overcome the issues of low conductivity, poor mechanical properties, and limited dimensions that are faced by conventional methods. The configurational design of advanced supercapacitor devices is presented with six types of unconventional supercapacitor devices: flexible, micro-, stretchable, compressible, transparent and fiber supercapacitors. Such supercapacitors display unique configurations and excellent electrochemical performance at different states such as bending, stretching, compressing and/or folding. For example, all-solid-state simplified supercapacitors that are based on nanostructured graphene composite paper are able to maintain 95% of the original capacity at a 180° folding state. The progress made so far will guide further developments in the structural design of nanocarbon-based electrode materials and the configurational diversity of supercapacitor devices. Future developments and prospects in the controllable assembly of macroscopic nanostructured electrodes and the innovation of unconventional supercapacitor configurations are also discussed. This should shed light on the R&D of supercapacitors.
TL;DR: UTSA-74a adsorbs a much smaller amount of carbon dioxide than Zn-MOF-74 at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation.
Abstract: A new metal-organic framework Zn2(H2O)(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 A. Unlike metal sites in the well-established MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn(2+) sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm(3)/cm(3)) to Zn-MOF-74. Interestingly, the accessible Zn(2+) sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm(3)/cm(3)) than Zn-MOF-74 (146 cm(3)/cm(3)) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result.
TL;DR: An intraparticle molecular orbital engineering approach to simultaneously enhance photoacoustic brightness and photothermal therapy efficacy of semiconducting polymer nanoparticles (SPNs) for in vivo imaging and treatment of cancer is reported.
Abstract: Optical theranostic nanoagents that seamlessly and synergistically integrate light-generated signals with photothermal or photodynamic therapy can provide opportunities for cost-effective precision medicine, while the potential for clinical translation requires them to have good biocompatibility and high imaging/therapy performance. We herein report an intraparticle molecular orbital engineering approach to simultaneously enhance photoacoustic brightness and photothermal therapy efficacy of semiconducting polymer nanoparticles (SPNs) for in vivo imaging and treatment of cancer. The theranostic SPNs have a binary optical component nanostructure, wherein a near-infrared absorbing semiconducting polymer and an ultrasmall carbon dot (fullerene) interact with each other to induce photoinduced electron transfer upon light irradiation. Such an intraparticle optoelectronic interaction augments heat generation and consequently enhances the photoacoustic signal and maximum photothermal temperature of SPNs by 2.6- a...
TL;DR: This work reports a molecular copper-porphyrin complex that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media and represents the highest catalytic activity to date for hydrocarbon production over a molecular CO2 reduction Electrocatalyst.
Abstract: Exploration of heterogeneous molecular catalysts combining the atomic-level tunability of molecular structures and the practical handling advantages of heterogeneous catalysts represents an attractive approach to developing high-performance catalysts for important and challenging chemical reactions such as electrochemical carbon dioxide reduction which holds the promise for converting emissions back to fuels utilizing renewable energy. Thus, far, efficient and selective electroreduction of CO2 to deeply reduced products such as hydrocarbons remains a big challenge. Here, we report a molecular copper-porphyrin complex (copper(II)-5,10,15,20-tetrakis(2,6-dihydroxyphenyl)porphyrin) that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media. At −0.976 V vs the reversible hydrogen electrode, the catalyst is able to drive partial current densities of 13.2 and 8.4 mA cm–2 for methane and ethylene production from CO2 reduction, correspo...
TL;DR: A facile solvothermal method to in situ decorate cobalt sulfide nanoplates on reduced graphene oxide (rGO) to build CoS@rGO composite is described, providing a facile approach to fabricate promising anode materials for high-performance SIBs.
Abstract: Exploitation of high-performance anode materials is essential but challenging to the development of sodium-ion batteries (SIBs). Among all proposed anode materials for SIBs, sulfides have been proved promising candidates due to their unique chemical and physical properties. In this work, a facile solvothermal method to in situ decorate cobalt sulfide (CoS) nanoplates on reduced graphene oxide (rGO) to build CoS@rGO composite is described. When evaluated as anode for SIBs, an impressive high specific capacity (540 mAh g(-1) at 1 A g(-1) ), excellent rate capability (636 mAh g(-1) at 0.1 A g(-1) and 306 mAh g(-1) at 10 A g(-1)), and extraordinarily cycle stability (420 mAh g(-1) at 1 A g(-1) after 1000 cycles) have been demonstrated by CoS@rGO composite for sodium storage. The synergetic effect between the CoS nanoplates and rGO matrix contributes to the enhanced electrochemical performance of the hybrid composite. The results provide a facile approach to fabricate promising anode materials for high-performance SIBs.
TL;DR: P palladium-catalyzed bidentate auxiliary-directed C-H functionalization reactions for αAA substrates enable new retrosynthetic logic for the synthesis of many basic αAAs from a common alanine precursor and may facilitate the efficient total synthesis of complex peptide natural products.
Abstract: α-Amino acids (αAA) are one of the most useful chiral building blocks for synthesis. There are numerous general strategies that have commonly been used for αAA synthesis, many of which employ de novo synthesis focused on enantioselective bond construction around the Cα center and others that consider conversion of existing αAA precursors carrying suitable functional groups on side chains (e.g., serine and aspartic acid). Despite significant advances in synthetic methodology, the efficient synthesis of enantiopure αAAs carrying complex side chains, as seen in numerous peptide natural products, remains challenging. Complementary to these "conventional" strategies, a strategy based on the selective functionalization of side chain C-H bonds, particularly sp(3) hybridized C-H bonds, of various readily available αAA precursors may provide a more straightforward and broadly applicable means for the synthesis and transformation of αAAs. However, many hurdles related to the low reactivity of C(sp(3))-H bonds and the difficulty of controlling selectivity must be overcome to realize the potential of C-H functionalization chemistry in this synthetic application. Over the past few years, we have carried out a systematic investigation of palladium-catalyzed bidentate auxiliary-directed C-H functionalization reactions for αAA substrates. Our strategies utilize two different types of amide-linked auxiliary groups, attached at the N or C terminus of αAA substrates, to exert complementary regio- and stereocontrol on C-H functionalization reactions through palladacycle intermediates. A variety of αAA precursors can undergo multiple modes of C(sp(3))-H functionalization, including arylation, alkenylation, alkynylation, alkylation, alkoxylation, and intramolecular aminations, at the β, γ, and even δ positions to form new αAA products with diverse structures. In addition to transforming αAAs at previously unreachable positions, these palladium-catalyzed C-H functionalization strategies enable new retrosynthetic logic for the synthesis of many basic αAAs from a common alanine precursor. This approach reduces the synthetic difficulty for many αAAs by bypassing the requirement for stereocontrol at Cα and relies on straightforward and convergent single-bond coupling transformations at the β-methyl position of alanine to access a wide range of β-monosubstituted αAAs. Moreover, these β-monosubstituted αAAs can undergo further C-H functionalization at the β-methylene position to generate various β-branched αAAs in a stereoselective and programmable fashion. These new strategies offer readily applicable methods for synthesis of challenging αAAs and may facilitate the efficient total synthesis of complex peptide natural products.
TL;DR: In this article, a facile nitrogenation/exfoliation process was used to prepare hybrid Ni-C-N nanosheets, which are <2 nm thin, chemically stable, and metallically conductive.
Abstract: We report a facile nitrogenation/exfoliation process to prepare hybrid Ni–C–N nanosheets. These nanosheets are <2 nm thin, chemically stable, and metallically conductive. They serve as a robust catalyst for the hydrogen evolution reaction in 0.5 M H2SO4, or 1.0 M KOH or 1.0 M PBS (pH = 7). For example, they catalyze the hydrogen evolution reaction in 0.5 M H2SO4 at an onset potential of 34.7 mV, an overpotential of 60.9 mV (at j = 10 mA cm–2) and with remarkable long-term stability (∼10% current drop after 70 h testing period). They are promising as a non-Pt catalyst for practical hydrogen evolution reaction.
TL;DR: In this paper, a series of GFs with various chemical compositions and physical structures have been prepared via a facile and controllable method and their MA performance is investigated in 2-18 GHz.
TL;DR: This tutorial review summarizes recent progress in this newly emerging field of metal-organic frameworks and constrain the local coordination geometries of lanthanide centers to represent two key factors governing the magnetic properties of molecular nanomagnets.
Abstract: Single-molecule magnets (SMMs) and single-chain magnets (SCMs), also known as molecular nanomagnets, are molecular species of nanoscale proportions with the potential for high information storage density and spintronics applications. Metal–organic frameworks (MOFs) are three-dimensional ordered assemblies of inorganic nodes and organic linkers, featuring structural diversity and multiple chemical and physical properties. The concept of using these frameworks as scaffolds in the study of molecular nanomagnets provides an opportunity to constrain the local coordination geometries of lanthanide centers and organize the individual magnetic building blocks (MBBs, including both transition-metal and lanthanide MBBs) into topologically well-defined arrays that represent two key factors governing the magnetic properties of molecular nanomagnets. In this tutorial review, we summarize recent progress in this newly emerging field.
TL;DR: Considering that the high capacity, long-term cycle life, and high-rate capability of anode materials for sodium-ion batteries (SIBs) is a bottleneck currently, a series of Co-doped FeS2 solid solutions with different Co contents were prepared by a facile solvothermal method, and for the first time their Na-storage properties were investigated.
Abstract: Considering that the high capacity, long-term cycle life, and high-rate capability of anode materials for sodium-ion batteries (SIBs) is a bottleneck currently, a series of Co-doped FeS2 solid solutions with different Co contents were prepared by a facile solvothermal method, and for the first time their Na-storage properties were investigated. The optimized Co0.5Fe0.5S2 (Fe0.5) has discharge capacities of 0.220 Ah g−1 after 5000 cycles at 2 A g−1 and 0.172 Ah g−1 even at 20 A g−1 with compatible ether-based electrolyte in a voltage window of 0.8–2.9 V. The Fe0.5 sample transforms to layered NaxCo0.5Fe0.5S2 by initial activation, and the layered structure is maintained during following cycles. The redox reactions of NaxCo0.5Fe0.5S2 are dominated by pseudocapacitive behavior, leading to fast Na+ insertion/extraction and durable cycle life. A Na3V2(PO4)3/Fe0.5 full cell was assembled, delivering an initial capacity of 0.340 Ah g−1.
TL;DR: The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application and gives high resolution for the separation of enantiomers with excellent repeatability and reproducibility.
Abstract: Covalent organic frameworks (COFs) are a novel class of porous materials, and offer great potential for various applications. However, the applications of COFs in chiral separation and chiral catalysis are largely underexplored due to the very limited chiral COFs available and their challenging synthesis. Here we show a bottom-up strategy to construct chiral COFs and an in situ growth approach to fabricate chiral COF-bound capillary columns for chiral gas chromatography. We incorporate the chiral centres into one of the organic ligands for the synthesis of the chiral COFs. We subsequently in situ prepare the COF-bound capillary columns. The prepared chiral COFs and their bound capillary columns give high resolution for the separation of enantiomers with excellent repeatability and reproducibility. The proposed strategy provides a promising platform for the synthesis of chiral COFs and their chiral separation application.
TL;DR: In this paper, an Ag/g-C3N4 composite photocatalyst, which was synthesized by thermal polymerization of melamine precursor combined with the photo-assisted reduction method, was applied as an efficient visible-light-driven photatalyst for inactivating Escherichia coli (E. coli).
Abstract: Ag/g-C3N4 composite photocatalyst, which was synthesized by thermal polymerization of melamine precursor combined with the photo-assisted reduction method, was applied as an efficient visible-light-driven photocatalyst for inactivating Escherichia coli (E. coli). The composite photocatalysts exhibited significantly enhanced photocatalytic disinfection efficiency than pure g-C3N4 powders. The mechanism of enhanced disinfection activity was systematically investigated by UV–visible diffuse reflectance spectra, photoluminescence spectra, and photo-electrochemical methods including photogenerated current densities, electrochemical impedance spectroscopy (EIS) spectra and Mott–Schottky plots. The enhanced photocatalytic bactericidal effect was attributed to the hybrid effect from Ag and g-C3N4, which resulted in enhanced adsorption of visible light, reduced recombination of free charges, rapid separation and transportation of photogenerated electrons–holes. The disinfection mechanism was studied by employing chemical scavengers and ESR technology, indicating the important role of h+ and e−. Considering the bulk availability and excellent disinfection activity of Ag/g-C3N4, it is a promising solar-driven photocatalyst for cleaning microbial contaminated water in practice.
TL;DR: The significantly improved electrochemical performance could be attributed to the unique structure that combines a variety of advantages: easy access of electrolyte to the open channel structure, short transport path of ions through carbon toward the red P, and high ionic and electronic conductivity.
Abstract: Red phosphorus (P) have been considered as one of the most promising anode material for both lithium-ion batteries (LIBs) and (NIBs), because of its high theoretical capacity. However, natural insulating property and the large volume expansion of red P during cycling lead to poor cyclability and low rate performance, which prevents its practical application. Here, we significantly improves both lithium storage and sodium storage performance of red P by confining nanosized amorphous red P into the mesoporous carbon matrix (P@CMK-3) using a vaporization-condensation-conversion process. The P@CMK-3 shows a high reversible specific capacity of ∼ 2250 mA h g(-1) based on the mass of red P at 0.25 C (∼ 971 mA h g(-1) based on the composite), excellent rate performance of 1598 and 624 mA h g(-1) based on the mass of red P at 6.1 and 12 C, respectively (562 and 228 mA h g(-1) based on the mass of the composite at 6.1 and 12 C, respectively) and significantly enhanced cycle life of 1150 mA h g(-1) based on the mass of red P at 5 C (500 mA h g(-1) based on the mass of the composite) after 1000 cycles for LIBs. For Na ions, it also displays a reversible capacity of 1020 mA h g(-1) based on the mass of red P (370 mA h g(-1) based on the mass of the composite) after 210 cycles at 5C. The significantly improved electrochemical performance could be attributed to the unique structure that combines a variety of advantages: easy access of electrolyte to the open channel structure, short transport path of ions through carbon toward the red P, and high ionic and electronic conductivity.
TL;DR: The distinctive structure of very-fine MnFe2O4 nanodots embedded in porous N-doped carbon nanofibers effectively improves the utilization rate of active materials, facilitates the transportation of electrons and Na(+) ions, and prevents the particle pulverization/agglomeration upon prolonged cycling.
Abstract: MnFe2O4 nanodots (∼3.3 nm) homogeneously dispersed in porous nitrogen-doped carbon nanofibers (denoted as MFO@C) were prepared by a feasible electrospinning technique. Meanwhile, MFO@C with the character of flexible free-standing membrane was directly used as binder- and current collector-free anode for sodium-ion batteries, exhibiting high electrochemical performance with high-rate capability (305 mA h g–1 at 10000 mA g–1 in comparison of 504 mA h g–1 at 100 mA g–1) and ultralong cycling life (ca. 90% capacity retention after 4200 cycles). The Na-storage mechanism was systematically studied, revealing that MnFe2O4 is converted into metallic Mn and Fe after the first discharge (MnFe2O4 + 8Na+ + 8e– → Mn + 2Fe + 4Na2O) and then to MnO and Fe2O3 during the following charge (Mn + 2Fe + 4Na2O → MnO + Fe2O3 + 8Na+ + 8e–). The subsequent cycles occur through reversible redox reactions of MnO + Fe2O3 + 8Na+ + 8e– ↔ Mn + 2Fe + 4Na2O, of which the reduction/oxidation of MnO/Mn takes place at a lower potential than...
TL;DR: An optimization problem formulation that aims at minimizing the time-average energy consumption for task executions of all users, meanwhile taking into account the incentive constraints of preventing the over-exploiting and free-riding behaviors which harm user's motivation for collaboration is proposed.
Abstract: In this paper, we propose device-to-device (D2D) Fogging, a novel mobile task offloading framework based on network-assisted D2D collaboration, where mobile users can dynamically and beneficially share the computation and communication resources among each other via the control assistance by the network operators. The purpose of D2D Fogging is to achieve energy efficient task executions for network wide users. To this end, we propose an optimization problem formulation that aims at minimizing the time-average energy consumption for task executions of all users, meanwhile taking into account the incentive constraints of preventing the over-exploiting and free-riding behaviors which harm user’s motivation for collaboration. To overcome the challenge that future system information such as user resource availability is difficult to predict, we develop an online task offloading algorithm, which leverages Lyapunov optimization methods and utilizes the current system information only. As the critical building block, we devise corresponding efficient task scheduling policies in terms of three kinds of system settings in a time frame. Extensive simulation results demonstrate that the proposed online algorithm not only achieves superior performance (e.g., it reduces approximately 30% ~ 40% energy consumption compared with user local execution), but also adapts to various situations in terms of task type, user amount, and task frequency.
TL;DR: This tutorial review focuses on the recent significant progress made in the domains of tissue regeneration and conversion & storage of clean energy and the advances in the use of electrospun materials for the removal of heavy metal ions, organic pollutants, gas and bacteria in water treatment applications.
Abstract: Tissue regeneration, energy conversion & storage, and water treatment are some of the most critical challenges facing humanity in the 21st century. In order to address such challenges, one-dimensional (1D) materials are projected to play a key role in developing emerging solutions for the increasingly complex problems. Eletrospinning technology has been demonstrated to be a simple, versatile, and cost-effective method in fabricating a rich variety of materials with 1D nanostructures. These include polymers, composites, and inorganic materials with unique chemical and physical properties. In this tutorial review, we first give a brief introduction to electrospun materials with a special emphasis on the design, fabrication, and modification of 1D functional materials. Adopting the perspective of chemists and materials scientists, we then focus on the recent significant progress made in the domains of tissue regeneration (e.g., skin, nerve, heart and bone) and conversion & storage of clean energy (e.g., solar cells, fuel cells, batteries, and supercapacitors), where nanofibres have been used as active nanomaterials. Furthermore, this review's scope also includes the advances in the use of electrospun materials for the removal of heavy metal ions, organic pollutants, gas and bacteria in water treatment applications. Finally a conclusion and perspective is provided, in which we discuss the remaining challenges for 1D electrospun nanomaterials in tissue regeneration, energy conversion & storage, and water treatment.
TL;DR: The mechanism of GO induced toxicity was determined, and in vitro experiments revealed that pristine GO could impair cell membrane integrity and functions including regulation of membrane- and cytoskeleton-associated genes, membrane permeability, fluidity and ion channels.
Abstract: The unique physicochemical properties of two-dimensional (2D) graphene oxide (GO) could greatly benefit the biomedical field; however, recent research demonstrated that GO could induce in vitro and in vivo toxicity. We determined the mechanism of GO induced toxicity, and our in vitro experiments revealed that pristine GO could impair cell membrane integrity and functions including regulation of membrane- and cytoskeleton-associated genes, membrane permeability, fluidity and ion channels. Furthermore, GO induced platelet depletion, pro-inflammatory response and pathological changes of lung and liver in mice. To improve the biocompatibility of pristine GO, we prepared a series of GO derivatives including aminated GO (GO-NH2), poly(acrylamide)-functionalized GO (GO-PAM), poly(acrylic acid)-functionalized GO (GO-PAA) and poly(ethylene glycol)-functionalized GO (GO-PEG), and compared their toxicity with pristine GO in vitro and in vivo. Among these GO derivatives, GO-PEG and GO-PAA induced less toxicity than pristine GO, and GO-PAA was the most biocompatible one in vitro and in vivo. The differences in biocompatibility were due to the differential compositions of protein corona, especially immunoglobulin G (IgG), formed on their surfaces that determine their cell membrane interaction and cellular uptake, the extent of platelet depletion in blood, thrombus formation under short-term exposure and the pro-inflammatory effects under long-term exposure. Overall, our combined data delineated the key molecular mechanisms underlying the in vivo and in vitro biological behaviors and toxicity of pristine GO, and identified a safer GO derivative that could be used for future applications.
TL;DR: Flexible nanostructured reduced graphene oxide-sulfur (rGO-S) composite films are fabricated by synchronously reducing and assembling GO sheets with S nanoparticles on a metal surface and can serve as the cathodes of flexible Li-S batteries.
Abstract: Flexible nanostructured reduced graphene oxide-sulfur (rGO-S) composite films are fabricated by synchronously reducing and assembling GO sheets with S nanoparticles on a metal surface. The nanostructured architecture in such composite films not only provides effective pathways for electron transport, but also suppresses the diffusion of polysulfides. Furthermore, they can serve as the cathodes of flexible Li-S batteries.