Showing papers by "Jilin University published in 2017"

Metal-Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy.

Abstract: Metal-organic frameworks (MOFs)-an emerging class of hybrid porous materials built from metal ions or clusters bridged by organic linkers-have attracted increasing attention in recent years. The superior properties of MOFs, such as well-defined pore aperture, tailorable composition and structure, tunable size, versatile functionality, high agent loading, and improved biocompatibility, make them promising candidates as drug delivery hosts. Furthermore, scientists have made remarkable achievements in the field of nanomedical applications of MOFs, owing to their facile synthesis on the nanoscale and alternative functionalization via inclusion and surface chemistry. A brief introduction to the applications of MOFs in controlled drug/cargo delivery and cancer therapy that have been reported in recent years is provided here.

Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and Renewable Energy Storage Using N2/NH3 Cycle

Abstract: Using tetrahexahedral gold nanorods as a heterogeneous electrocatalyst, an electrocatalytic N2 reduction reaction is shown to be possible at room temperature and atmospheric pressure, with a high Faradic efficiency up to 4.02% at -0.2 V vs reversible hydrogen electrode (1.648 µg h-1 cm-2 and 0.102 µg h-1 cm-2 for NH3 and N2 H4 ·H2 O, respectively).

Porous Organic Materials: Strategic Design and Structure–Function Correlation

Abstract: Porous organic materials have garnered colossal interest with the scientific fraternity due to their excellent gas sorption performances, catalytic abilities, energy storage capacities, and other intriguing applications. This review encompasses the recent significant breakthroughs and the conventional functions and practices in the field of porous organic materials to find useful applications and imparts a comprehensive understanding of the strategic evolution of the design and synthetic approaches of porous organic materials with tunable characteristics. We present an exhaustive analysis of the design strategies with special emphasis on the topologies of crystalline and amorphous porous organic materials. In addition to elucidating the structure–function correlation and state-of-the-art applications of porous organic materials, we address the challenges and restrictions that prevent us from realizing porous organic materials with tailored structures and properties for useful applications.

Au Sub-Nanoclusters on TiO2 toward Highly Efficient and Selective Electrocatalyst for N2 Conversion to NH3 at Ambient Conditions.

Abstract: As the NN bond in N2 is one of the strongest bonds in chemistry, the fixation of N2 to ammonia is a kinetically complex and energetically challenging reaction and, up to now, its synthesis is still heavily relying on energy and capital intensive Haber-Bosch process (150-350 atm, 350-550 °C), wherein the input of H2 and energy are largely derived from fossil fuels and thus result in large amount of CO2 emission. In this paper, it is demonstrated that by using Au sub-nanoclusters (≈0.5 nm ) embedded on TiO2 (Au loading is 1.542 wt%), the electrocatalytic N2 reduction reaction (NRR) is indeed possible at ambient condition. Unexpectedly, NRR with very high and stable production yield (NH3 : 21.4 µg h-1 mg-1cat. , Faradaic efficiency: 8.11%) and good selectivity is achieved at -0.2 V versus RHE, which is much higher than that of the best results for N2 fixation under ambient conditions, and even comparable to the yield and activation energy under high temperatures and/or pressures. As isolated precious metal active centers dispersed onto oxide supports provide a well-defined system, the special structure of atomic Au cluster would promote other important reactions besides NRR for water splitting, fuel cells, and other electrochemical devices.

Atomic Modulation of FeCo–Nitrogen–Carbon Bifunctional Oxygen Electrodes for Rechargeable and Flexible All-Solid-State Zinc–Air Battery

Abstract: Rational design and exploration of robust and low-cost bifunctional oxygen reduction/evolution electrocatalysts are greatly desired for metal–air batteries. Herein, a novel high-performance oxygen electrode catalyst is developed based on bimetal FeCo nanoparticles encapsulated in in situ grown nitrogen-doped graphitic carbon nanotubes with bamboo-like structure. The obtained catalyst exhibits a positive half-wave potential of 0.92 V (vs the reversible hydrogen electrode, RHE) for oxygen reduction reaction, and a low operating potential of 1.73 V to achieve a 10 mA cm−2 current density for oxygen evolution reaction. The reversible oxygen electrode index is 0.81 V, surpassing that of most highly active bifunctional catalysts reported to date. By combining experimental and simulation studies, a strong synergetic coupling between FeCo alloy and N-doped carbon nanotubes is proposed in producing a favorable local coordination environment and electronic structure, which affords the pyridinic N-rich catalyst surface promoting the reversible oxygen reactions. Impressively, the assembled zinc–air batteries using liquid electrolytes and the all-solid-state batteries with the synthesized bifunctional catalyst as the air electrode demonstrate superior charging–discharging performance, long lifetime, and high flexibility, holding great potential in practical implementation of new-generation powerful rechargeable batteries with portable or even wearable characteristic.

Highly Oriented Low-Dimensional Tin Halide Perovskites with Enhanced Stability and Photovoltaic Performance

Abstract: The low toxicity and a near-ideal choice of bandgap make tin perovskite an attractive alternative to lead perovskite in low cost solar cells. However, the development of Sn perovskite solar cells has been impeded by their extremely poor stability when exposed to oxygen. We report low-dimensional Sn perovskites that exhibit markedly enhanced air stability in comparison with their 3D counterparts. The reduced degradation under air exposure is attributed to the improved thermodynamic stability after dimensional reduction, the encapsulating organic ligands, and the compact perovskite film preventing oxygen ingress. We then explore these highly oriented low-dimensional Sn perovskite films in solar cells. The perpendicular growth of the perovskite domains between electrodes allows efficient charge carrier transport, leading to power conversion efficiencies of 5.94% without the requirement of further device structure engineering. We tracked the performance of unencapsulated devices over 100 h and found no apprec...

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

Abstract: Hybrid organic–inorganic halide perovskites with the prototype material of CH3NH3PbI3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues—the poor device stabilities associated with their intrinsic material instability and the toxicity due to water-soluble Pb2+—need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb2+ ions into one monovalent M+ and one trivalent M3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screen...

Near-Infrared Photoluminescent Polymer-Carbon Nanodots with Two-Photon Fluorescence

Abstract: Near-infrared-emissive polymer-carbon nanodots (PCNDs) are fabricated by a newly developed facile, high-output strategy. The PCNDs emit at a wavelength of 710 nm with a quantum yield of 26.28%, which is promising for deep biological imaging and luminescent devices. Moreover, the PCNDs possess two-photon fluorescence; in vivo bioimaging and red-light-emitting diodes based on these PCNDs are demonstrated.

PixelDefend: Leveraging Generative Models to Understand and Defend against Adversarial Examples

Abstract: Adversarial perturbations of normal images are usually imperceptible to humans, but they can seriously confuse state-of-the-art machine learning models. What makes them so special in the eyes of image classifiers? In this paper, we show empirically that adversarial examples mainly lie in the low probability regions of the training distribution, regardless of attack types and targeted models. Using statistical hypothesis testing, we find that modern neural density models are surprisingly good at detecting imperceptible image perturbations. Based on this discovery, we devised PixelDefend, a new approach that purifies a maliciously perturbed image by moving it back towards the distribution seen in the training data. The purified image is then run through an unmodified classifier, making our method agnostic to both the classifier and the attacking method. As a result, PixelDefend can be used to protect already deployed models and be combined with other model-specific defenses. Experiments show that our method greatly improves resilience across a wide variety of state-of-the-art attacking methods, increasing accuracy on the strongest attack from 63% to 84% for Fashion MNIST and from 32% to 70% for CIFAR-10.

Progress in the treatment of advanced gastric cancer

Abstract: Gastric cancer is one of the most common malignant tumors in the digestive system. Surgery is currently considered to be the only radical treatment. As surgical techniques improve and progress is made in traditional radiotherapy, chemotherapy, and the implementation of neoadjuvant therapy, the 5-year survival rate of early gastric cancer can reach >95%. However, the low rate of early diagnosis means that most patients have advanced-stage disease at diagnosis and so the best surgical window is missed. Therefore, the main treatment for advanced gastric cancer is the combination of neoadjuvant chemoradiotherapy, molecular-targeted therapy, and immunotherapy. In this article, we summarize several common methods used to treat advanced gastric cancer and discuss the progress made in the treatment of gastric cancer in detail. Only clinical practice and clinical research will allow us to prolong the survival time of patients and allow the patients to truly benefit by paying attention to the individual patient cha...

Hydrogen Clathrate Structures in Rare Earth Hydrides at High Pressures: Possible Route to Room-Temperature Superconductivity.

Abstract: We acknowledge funding support from Science Challenge Project at Grant No. TZ2016001, the National Natural Science Foundation of China under Grant No. 11534003, and the National Key Research and Development Program of China under Grant No. 2016YFB0201200. We also thank China Postdoctoral Science Foundation under Grant No. 2016M590033, the Natural Science Foundation of Henan Province Grant No. 162300410199, the Program for Science and Technology Innovation Talents in University of Henan Province Grant No. 17HASTIT015, and the Open Project of the State Key Laboratory of Superhard Materials, Jilin University, under Grant No. 201602. R. J. N. acknowledges funding from the Engineering and Physical Sciences Research Council (EPSRC) of the UK under Grant No. EP/J017639/1. C. J. P. is supported by a Royal Society Wolfson Research Merit Award. Computational resources were provided by the high performance computing center of Jilin University, Tianhe2-JK in the Beijing Computational Science Research Center, the High Performance Computing Service at the University of Cambridge, and the ARCHER facility of the UK’s national high-performance computing service, for which access was obtained via the UKCP consortium (Grant No. EP/P022596/1).

Amorphizing of Au Nanoparticles by CeOx -RGO Hybrid Support towards Highly Efficient Electrocatalyst for N2 Reduction under Ambient Conditions.

Abstract: Ammonia synthesis is one of the most kinetically complex and energetically challenging chemical processes in industry and has used the Harber-Bosch catalyst for over a century, which is processed under both harsh pressure (150-350 atm) and hightemperature (623-823 K), wherein the energy and capital intensive Harber-Bosch process has a huge energy cost accounting for about 1%-3% of human's energy consumption. Therefore, there has been a rough and vigorous exploration to find an environmentally benign alternative process. As the amorphous material is in a metastable state and has many "dangling bonds", it is more active than the crystallized one. In this paper, CeOx -induced amorphization of Au nanoparticles anchored on reduced graphite oxide (a-Au/CeOx -RGO) has been achieved by a facile coreduction method under ambient atmosphere. As a proof-of-concept experiment, a-Au/CeOx -RGO hybrid catalyst containing the low noble metal (Au loading is 1.31 wt%) achieves a high Faradaic efficiency (10.10%) and ammonia yield (8.3 μg h-1 mg-1cat. ) at -0.2 V versus RHE, which is significantly higher than that of the crystalline counterpart (c-Au/RGO), and even comparable to the yields and efficiencies under harsh temperatures and/or pressures.

Enhanced Cisplatin Chemotherapy by Iron Oxide Nanocarrier-Mediated Generation of Highly Toxic Reactive Oxygen Species.

Abstract: Reactive oxygen species (ROS) plays a key role in therapeutic effects as well as side effects of platinum drugs. Cisplatin mediates activation of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX), which triggers oxygen (O2) to superoxide radical (O2•–) and its downstream H2O2. Through the Fenton’s reaction, H2O2 could be catalyzed by Fe2+/Fe3+ to the toxic hydroxyl radicals (•OH), which cause oxidative damages to lipids, proteins, and DNA. By taking the full advantage of Fenton’s chemistry, we herein demonstrated tumor site-specific conversion of ROS generation induced by released cisplatin and Fe2+/Fe3+ from iron-oxide nanocarriers with cisplatin(IV) prodrugs for enhanced anticancer activity but minimized systemic toxicity.

Induction of tumor apoptosis through a circular RNA enhancing Foxo3 activity

Abstract: Circular RNAs are a class of non-coding RNAs that are receiving extensive attention. Despite reports showing circular RNAs acting as microRNA sponges, the biological functions of circular RNAs remain largely unknown. We show that in patient tumor samples and in a panel of cancer cells, circ-Foxo3 was minimally expressed. Interestingly, during cancer cell apoptosis, the expression of circ-Foxo3 was found to be significantly increased. We found that silencing endogenous circ-Foxo3 enhanced cell viability, whereas ectopic expression of circ-Foxo3 triggered stress-induced apoptosis and inhibited the growth of tumor xenografts. Also, expression of circ-Foxo3 increased Foxo3 protein levels but repressed p53 levels. By binding to both, circ-Foxo3 promoted MDM2-induced p53 ubiquitination and subsequent degradation, resulting in an overall decrease of p53. With low binding affinity to Foxo3 protein, circ-Foxo3 prevented MDM2 from inducing Foxo3 ubiquitination and degradation, resulting in increased levels of Foxo3 protein. As a result, cell apoptosis was induced by upregulation of the Foxo3 downstream target PUMA.

Social Collaborative Filtering by Trust

Abstract: Recommender systems are used to accurately and actively provide users with potentially interesting information or services. Collaborative filtering is a widely adopted approach to recommendation, but sparse data and cold-start users are often barriers to providing high quality recommendations. To address such issues, we propose a novel method that works to improve the performance of collaborative filtering recommendations by integrating sparse rating data given by users and sparse social trust network among these same users. This is a model-based method that adopts matrix factorization technique that maps users into low-dimensional latent feature spaces in terms of their trust relationship, and aims to more accurately reflect the users reciprocal influence on the formation of their own opinions and to learn better preferential patterns of users for high-quality recommendations. We use four large-scale datasets to show that the proposed method performs much better, especially for cold start users, than state-of-the-art recommendation algorithms for social collaborative filtering based on trust.

CsPbxMn1–xCl3 Perovskite Quantum Dots with High Mn Substitution Ratio

Abstract: CsPbX3 (X = Cl, Br, I) perovskite quantum dots (QDs) are potential emitting materials for illumination and display applications, but toxic Pb is not environment- and user-friendly. In this work, we demonstrate the partial replacement of Pb with Mn through phosphine-free hot-injection preparation of CsPbxMn1–xCl3 QDs in colloidal solution. The Mn substitution ratio is up to 46%, and the as-prepared QDs maintain the tetragonal crystalline structure of the CsPbCl3 host. Meaningfully, Mn substitution greatly enhances the photoluminescence quantum yields of CsPbCl3 from 5 to 54%. The enhanced emission is attributed to the energy transfer of photoinduced excitons from the CsPbCl3 host to the doped Mn, which facilitates exciton recombination via a radiative pathway. The intensity and position of this Mn-related emission are also tunable by altering the experimental parameters, such as reaction temperature and the Pb-to-Mn feed ratio. A light-emitting diode (LED) prototype is further fabricated by employing the a...

Ultrafast Formation of Amorphous Bimetallic Hydroxide Films on 3D Conductive Sulfide Nanoarrays for Large-Current-Density Oxygen Evolution Electrocatalysis.

Abstract: Developing nonprecious oxygen evolution electrocatalysts that can work well at large current densities is of primary importance in a viable water-splitting technology. Herein, a facile ultrafast (5 s) synthetic approach is reported that produces a novel, efficient, non-noble metal oxygen-evolution nano-electrocatalyst that is composed of amorphous Ni-Fe bimetallic hydroxide film-coated, nickel foam (NF)-supported, Ni3 S2 nanosheet arrays. The composite nanomaterial (denoted as Ni-Fe-OH@Ni3 S2 /NF) shows highly efficient electrocatalytic activity toward oxygen evolution reaction (OER) at large current densities, even in the order of 1000 mA cm-2 . Ni-Fe-OH@Ni3 S2 /NF also gives an excellent catalytic stability toward OER both in 1 m KOH solution and in 30 wt% KOH solution. Further experimental results indicate that the effective integration of high catalytic reactivity, high structural stability, and high electronic conductivity into a single material system makes Ni-Fe-OH@Ni3 S2 /NF a remarkable catalytic ability for OER at large current densities.

Materials discovery at high pressures

Abstract: Pressure is a fundamental thermodynamic variable that can be used to control the properties of materials, because it reduces interatomic distances and profoundly modifies electronic orbitals and bonding patterns. It is thus a versatile tool for the creation of exotic materials not accessible at ambient conditions. Recently developed static and dynamic high-pressure experimental techniques have led to the synthesis of many functional materials with excellent performance: for example, superconductors, superhard materials and high-energy-density materials. Some of these advances have been aided and accelerated by first-principles crystal-structure searching simulations. In this Review, we discuss recent progress in high-pressure materials discovery, placing particular emphasis on the record high-temperature superconductivity in hydrogen sulfide and on nanotwinned cubic boron nitride and diamond, the hardest known materials. Energy materials and exotic chemical materials obtained under high pressures are also discussed. The main drawback of high-pressure materials is their destabilization after pressure release; this problem and its possible solutions are surveyed in the conclusions, which also provide an outlook on the future developments in the field. High pressure offers a unique degree of freedom for the creation of new materials, leading to new superconductors, superhard materials, high-energy-density materials and exotic chemical materials with unprecedented properties. This Review discusses these materials, along with recently developed theoretical and experimental methods for materials discovery at high pressures.

Complement proteins bind to nanoparticle protein corona and undergo dynamic exchange in vivo

Abstract: Immune proteins bind to protein corona on core-shell nanoparticles and undergo dynamic exchange in vivo.

The Role of Neural Plasticity in Depression: From Hippocampus to Prefrontal Cortex.

Abstract: Neural plasticity, a fundamental mechanism of neuronal adaptation, is disrupted in depression. The changes in neural plasticity induced by stress and other negative stimuli play a significant role in the onset and development of depression. Antidepressant treatments have also been found to exert their antidepressant effects through regulatory effects on neural plasticity. However, the detailed mechanisms of neural plasticity in depression still remain unclear. Therefore, in this review, we summarize the recent literature to elaborate the possible mechanistic role of neural plasticity in depression. Taken together, these findings may pave the way for future progress in neural plasticity studies.

Towards High-Safe Lithium Metal Anodes: Suppressing Lithium Dendrites via Tuning Surface Energy

Abstract: The formation of lithium dendrites induces the notorious safety issue and poor cycling life of energy storage devices, such as lithium–sulfur and lithium–air batteries. We propose a surface energy model to describe the complex interface between the lithium anode and electrolyte. A universal strategy of hindering formation of lithium dendrites via tuning surface energy of the relevant thin film growth is suggested. The merit of the novel motif lies not only fundamentally a perfect correlation between electrochemistry and thin film fields, but also significantly promotes larger-scale application of lithium–sulfur and lithium–air batteries, as well as other metal batteries (e.g., Zn, Na, K, Cu, Ag, and Sn).

High-Efficiency and Air-Stable Perovskite Quantum Dots Light-Emitting Diodes with an All-Inorganic Heterostructure

Abstract: Perovskite light-emitting diodes (PeLEDs), because of its fundamental scientific importance and practical applications in the fields of low-cost light source or display applications, have drawn worldwide attention in recent years. However, PeLEDs available today suffer from a compromise in their emission efficiency and operation stability. In this study, we designed and fabricated a stacking all-inorganic multilayer structure by using inorganic perovskite CsPbBr3 quantum dots (QDs) as the emissive layer and inorganic n-type MgZnO and p-type MgNiO as the carrier injectors, respectively. Through energy band engineering of carrier injectors by Mg incorporation and their thickness optimization, PeLEDs with maximum luminance of 3809 cd/m2, luminous efficiency of 2.25 cd/A, and external quantum efficiency of 2.39% have been realized, which are much better than most PeLEDs from CH3NH3PbBr3 films, and comparable with the highest results reported on CsPbBr3 QDs LEDs. More importantly, the unencapsulated PeLEDs in ...

Coupling Sub-Nanometric Copper Clusters with Quasi-Amorphous Cobalt Sulfide Yields Efficient and Robust Electrocatalysts for Water Splitting Reaction

Abstract: Superefficient water-splitting materials comprising sub-nanometric copper clusters and quasi-amorphous cobalt sulfide supported on copper foam are reported. While working together at both the anode and cathode sides of an alkaline electrolyzer, this material gives a catalytic output of overall water splitting comparable with the Pt/C-IrO2 -coupled electrolyzer.

The Link between Depression and Chronic Pain: Neural Mechanisms in the Brain

Abstract: Chronic pain, as a stress state, is one of the critical factors for determining depression, and their coexistence tends to further aggravate the severity of both disorders. Unfortunately, their association remains unclear, which creates a bottleneck problem for managing chronic pain-induced depression. In recent years, studies have found considerable overlaps between pain- and depression-induced neuroplasticity changes and neurobiological mechanism changes. Such overlaps are vital to facilitating the occurrence and development of chronic pain and chronic pain-induced depression. In this review, we summarized the role of neuroplasticity in the occurrence and development of the two disorders in question and explored individualized application strategies of analgesic drugs and antidepressants that have different pharmacological effects in the treatment of chronic pain-induced depression. Therefore, this review may provide new insights into the understanding of association between chronic pain and depression.

Cerium and Ytterbium Codoped Halide Perovskite Quantum Dots: A Novel and Efficient Downconverter for Improving the Performance of Silicon Solar Cells.

Abstract: Quantum cutting can realize the emission of multiple near-infrared photons for each ultraviolet/visible photon absorbed, and has potential to significantly improve the photoelectric conversion efficiency (PCE) of solar cells. However, due to the lack of an ideal downconversion material, it has merely served as a principle in the laboratory until now. Here, the fabrication of a novel type of quantum cutting material, CsPbCl1.5 Br1.5 :Yb3+ , Ce3+ nanocrystals is presented. Benefiting from the larger absorption cross-section, weaker electron-phonon coupling, and higher inner luminescent quantum yield (146%), the doped perovskite nanocrystals are successfully explored as a downconverter of commercial silicon solar cells (SSCs). Noticeably, the PCE of the SSCs is improved from 18.1% to 21.5%, with a relative enhancement of 18.8%. This work exhibits a cheap, convenient, and effective way to enhance the PCE of SSCs, which may be commercially popularized in the future.