Showing papers by "Jun Lu published in 2016"

Linkers Having a Crucial Role in Antibody-Drug Conjugates.

Abstract: Antibody-drug conjugates (ADCs) comprised of a desirable monoclonal antibody, an active cytotoxic drug and an appropriate linker are considered to be an innovative therapeutic approach for targeted treatment of various types of tumors and cancers, enhancing the therapeutic parameter of the cytotoxic drug and reducing the possibility of systemic cytotoxicity. An appropriate linker between the antibody and the cytotoxic drug provides a specific bridge, and thus helps the antibody to selectively deliver the cytotoxic drug to tumor cells and accurately releases the cytotoxic drug at tumor sites. In addition to conjugation, the linkers maintain ADCs' stability during the preparation and storage stages of the ADCs and during the systemic circulation period. The design of linkers for ADCs is a challenge in terms of extracellular stability and intracellular release, and intracellular circumstances, such as the acid environment, the reducing environment and cathepsin, are considered as the catalysts to activate the triggers for initiating the cleavage of ADCs. This review discusses the linkers used in the clinical and marketing stages for ADCs and details the fracture modes of the linkers for the further development of ADCs.

The influence of large cations on the electrochemical properties of tunnel-structured metal oxides

Abstract: Metal oxides with a tunnelled structure are attractive as charge storage materials for rechargeable batteries and supercapacitors, since the tunnels enable fast reversible insertion/extraction of charge carriers (for example, lithium ions). Common synthesis methods can introduce large cations such as potassium, barium and ammonium ions into the tunnels, but how these cations affect charge storage performance is not fully understood. Here, we report the role of tunnel cations in governing the electrochemical properties of electrode materials by focusing on potassium ions in α-MnO2. We show that the presence of cations inside 2 × 2 tunnels of manganese dioxide increases the electronic conductivity, and improves lithium ion diffusivity. In addition, transmission electron microscopy analysis indicates that the tunnels remain intact whether cations are present in the tunnels or not. Our systematic study shows that cation addition to α-MnO2 has a strong beneficial effect on the electrochemical performance of this material.

Tuning of Thermal Stability in Layered Li(NixMnyCoz)O2

Abstract: Understanding and further designing new layered Li(NixMnyCoz)O2 (NMC) (x + y + z = 1) materials with optimized thermal stability is important to rechargeable Li batteries (LIBs) for electrical vehicles (EV). Using ab initio calculations combined with experiments, we clarified how the thermal stability of NMC materials can be tuned by the most unstable oxygen, which is determined by the local coordination structure unit (LCSU) of oxygen (TM(Ni, Mn, Co)3-O-Li3–x′): each O atom bonds with three transition metals (TM) from the TM-layer and three to zero Li from fully discharged to charged states from the Li-layer. Under this model, how the lithium content, valence states of Ni, contents of Ni, Mn, and Co, and Ni/Li disorder to tune the thermal stability of NMC materials by affecting the sites, content, and the release temperature of the most unstable oxygen is proposed. The synergistic effect between Li vacancies and raised valence state of Ni during delithiation process can aggravate instability of oxygen, a...

High Capacity of Hard Carbon Anode in Na-Ion Batteries Unlocked by POx Doping

Abstract: The capacity of hard carbon anodes in Na-ion batteries rarely reaches values beyond 300 mAh/g. We report that doping POx into local structures of hard carbon increases its reversible capacity from 283 to 359 mAh/g. We confirm that the doped POx is redox inactive by X-ray adsorption near edge structure measurements, thus not contributing to the higher capacity. We observe two significant changes of hard carbon’s local structures caused by doping. First, the (002) d-spacing inside the turbostratic nanodomains is increased, revealed by both laboratory and synchrotron X-ray diffraction. Second, doping turns turbostratic nanodomains more defective along ab planes, indicated by neutron total scattering and the associated pair distribution function studies. The local structural changes of hard carbon are correlated to the higher capacity, where both the plateau and slope regions in the potential profiles are enhanced. Our study demonstrates that Na-ion storage in hard carbon heavily depends on carbon local struc...

Synthesis and Characterization of an Alumina Forming Nanolaminated Boride: MoAlB.

Abstract: The ‘MAlB’ phases are nanolaminated, ternary transition metal borides that consist of a transition metal boride sublattice interleaved by monolayers or bilayers of pure aluminum. However, their synthesis and properties remain largely unexplored. Herein, we synthesized dense, predominantly single-phase samples of one such compound, MoAlB, using a reactive hot pressing method. High-resolution scanning transmission electron microscopy confirmed the presence of two Al layers in between a Mo-B sublattice. Unique among the transition metal borides, MoAlB forms a dense, alumina scale when heated in air. Like other alumina formers, the oxidation kinetics follow a cubic time-dependence. At room temperature, its resistivity is low (0.36–0.49 μΩm) and – like a metal – drops linearly with decreasing temperatures. It is also a good thermal conductor (35 Wm−1K−1 at 26 °C). In the 25–1300 °C temperature range, its thermal expansion coefficient is 9.5 × 10−6K−1. Preliminary results suggest the compound is stable to at least 1400 °C in inert atmospheres. Moderately low Vickers hardness values of 10.6 ± 0.3 GPa, compared to other transition metal borides, and ultimate compressive strengths up to 1940 ± 103 MPa were measured at room temperature. These results are encouraging and warrant further study of this compound for potential use at high temperatures.

Freestanding three-dimensional core–shell nanoarrays for lithium-ion battery anodes

Abstract: Structural degradation and low conductivity of transition-metal oxides lead to severe capacity fading in lithium-ion batteries. Recent efforts to solve this issue have mainly focused on using nanocomposites or hybrids by integrating nanosized metal oxides with conducting additives. Here we design specific hierarchical structures and demonstrate their use in flexible, large-area anode assemblies. Fabrication of these anodes is achieved via oxidative growth of copper oxide nanowires onto copper substrates followed by radio-frequency sputtering of carbon-nitride films, forming freestanding three-dimensional arrays with core-shell nano-architecture. Cable-like copper oxide/carbon-nitride core-shell nanostructures accommodate the volume change during lithiation-delithiation processes, the three-dimensional arrays provide abundant electroactive zones and electron/ion transport paths, and the monolithic sandwich-type configuration without additional binders or conductive agents improves energy/power densities of the whole electrode.

Anion-redox nanolithia cathodes for Li-ion batteries

Abstract: The significant phase change between gaseous and crystalline oxygen deteriorates the performance of lithium–air batteries. Here the authors report a battery with a cathode consisting of Li2O and Co3O4 nanocomposites, which displays stable cyclability and high energy density, without involving any gas evolution.

In Operando XRD and TXM Study on the Metastable Structure Change of NaNi1/3Fe1/3Mn1/3O2 under Electrochemical Sodium-Ion Intercalation

Abstract: Y. Xie, Dr. H. Wang, Prof. Z.-F. Ma Department of Chemical Engineering Shanghai Jiao Tong University Shanghai 200240, China E-mail: zfma@sjtu.edu.cn Y. Xie, Dr. G. Xu, Dr. Z. Chen, Dr. J. Lu, Dr. K. Amine Chemical Sciences and Engineering Division Argonne National Laboratory 9700 South Cass Avenue, Lemont, IL 60439, USA E-mail: junlu@anl.gov; amine@anl.gov Dr. J. Wang, Dr. J. Wang Photon Sciences Directorate Brookhaven National Laboratory Building 744 Ring Road, Upton, NY 11973, USA Dr. H. Sheng, Dr. J. G. Wen, Dr. D. J. Miller Electron Microscopy Center – Center for Nanoscale Materials Argonne National Laboratory 9700 South Cass Avenue, Lemont, IL 60439, USA Dr. Y. Ren, Dr. C.-J. Sun Advanced Photon Source Argonne National Laboratory 9700 South Cass Avenue, Lemont, IL 60439, USA

Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life.

Abstract: The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li+-conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational ...

The microRNA miR-148a functions as a critical regulator of B cell tolerance and autoimmunity.

Abstract: Autoreactive B cells have critical roles in a large diversity of autoimmune diseases, but the molecular pathways that control these cells remain poorly understood. We performed an in vivo functional screen of a lymphocyte-expressed microRNA library and identified miR-148a as a potent regulator of B cell tolerance. Elevated miR-148a expression impaired B cell tolerance by promoting the survival of immature B cells after engagement of the B cell antigen receptor by suppressing the expression of the autoimmune suppressor Gadd45α, the tumor suppressor PTEN and the pro-apoptotic protein Bim. Furthermore, increased expression of miR-148a, which occurs frequently in patients with lupus and lupus-prone mice, facilitated the development of lethal autoimmune disease in a mouse model of lupus. Our studies demonstrate a function for miR-148a as a regulator of B cell tolerance and autoimmunity.

Application of Fused Deposition Modelling (FDM) Method of 3D Printing in Drug Delivery.

Abstract: Three-dimensional (3D) printing is an emerging manufacturing technology for biomedical and pharmaceutical applications Fused deposition modelling (FDM) is a low cost extrusion-based 3D printing technique that can deposit materials layer-by-layer to create solid geometries This review article aims to provide an overview of FDM based 3D printing application in developing new drug delivery systems The principle methodology, suitable polymers and important parameters in FDM technology and its applications in fabrication of personalised tablets and drug delivery devices are discussed in this review FDM based 3D printing is a novel and versatile manufacturing technique for creating customised drug delivery devices that contain accurate dose of medicine( s) and provide controlled drug released profiles

Synthesis of the new MAX phase Zr2AlC

Abstract: This study reports on the first experimental evidence of the existence of the Zr2AlC MAX phase, synthesised by means of reactive hot pressing of a ZrH2, Al and C powder mixture. The crystal structu ...

Solar-powered electrochemical energy storage: an alternative to solar fuels

Abstract: Because of the intermittent nature of solar radiation, being able to simultaneously convert and store solar energy is a significant advance for efficiently harnessing solar energy. Solar fuels have already been recognized as a promising method towards this goal and have attracted tremendous research interest recently. Alternatively, this goal can also be achieved by using the solar-powered electrochemical energy storage (SPEES) strategy, which integrates a photoelectrochemical cell and an electrochemical cell into a single device. The integrated device is able to harvest solar energy and store it in situ within the device via a photocharging process and also distribute the energy as electric power when needed. This essay reviews the past SPEES research and analyzes its future prospects with a special emphasis on chemical design and material choices. We hope that the article will help draw more research attention to this field and stimulate additional exciting investigations toward more efficient solar energy utilization.

Present Advances and Future Perspectives of Molecular Targeted Therapy for Osteosarcoma

Abstract: Osteosarcoma (OS) is a bone cancer mostly occurring in pediatric population. Current treatment regime of surgery and intensive chemotherapy could cure about 60%–75% patients with primary osteosarcoma, however only 15% to 30% can be cured when pulmonary metastasis or relapse has taken place. Hence, novel precise OS-targeting therapies are being developed with the hope of addressing this issue. This review summarizes the current development of molecular mechanisms and targets for osteosarcoma. Therapies that target these mechanisms with updated information on clinical trials are also reviewed. Meanwhile, we further discuss novel therapeutic targets and OS-targeting drug delivery systems. In conclusion, a full insight in OS pathogenesis and OS-targeting strategies would help us explore novel targeted therapies for metastatic osteosarcoma.

Synthesis of the novel Zr3AlC2 MAX phase

Abstract: Herein we report, for the first time, on the synthesis and structural characterization of the Zr-based MAX phase, Zr 3 AlC 2 , fabricated by reactive hot pressing of ZrH 2 , Al, and C powders. The crystal structure of Zr 3 AlC 2 was determined by X-ray diffraction and high resolution transmission electron microscopy to be the hexagonal space group P63/mmc . The a and c lattice parameters are 3.33308(6) A and 19.9507(3) A, respectively. The samples include the secondary phases ZrC and Zr–Al intermetallics as confirmed by quantitative electron probe microanalysis. The Vickers hardness, using a force of 30 N, was measured to be 4.4 ± 0.4 GPa.

Facile Synthesis of Boron-Doped rGO as Cathode Material for High Energy Li-O2 Batteries.

Abstract: To improve the electrochemical performance of the high energy Li–O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, a three-dimensional (3D) porous boron-doped reduction graphite oxide (B-rGO) material with a hierarchical structure has been prepared by a facile freeze-drying method. In this design, boric acid as the boron source helps to form the 3D porous structure, owing to its cross-linking and pore-forming function. This architecture facilitates the rapid oxygen diffusion and electrolyte penetration in the electrode. Meanwhile, the boron–oxygen functional groups linking to the carbon surface or edge serve as additional reaction sites to activate the ORR process. It is vital that boron atoms have been doped into the carbon lattices to greatly activate the electrons in the carbon π system, which is beneficial for fast charge under large current densities. Density functional theory calculation demonstrates that B-rGO exhibits much stronger int...

Platinum‐Coated Hollow Graphene Nanocages as Cathode Used in Lithium‐Oxygen Batteries

Abstract: One of the formidable challenges facing aprotic lithium-oxygen (Li-O2) batteries is the high charge overpotential, which induces the formation of byproducts, loss in efficiency, and poor cycling performance. Herein, the synthesis of the ultrasmall Pt-coated hollow graphene nanocages as cathode in Li-O2 batteries is reported. The charge voltage plateau can reduce to 3.2 V at the current density of 100 mA g−1, even maintain below 3.5 V when the current density increased to 500 mA g−1. The unique hollow graphene nanocages matrix can not only provide numerous nanoscale tri-phase regions as active sites for efficient oxygen reduction, but also offer sufficient amount of mesoscale pores for rapid oxygen diffusion. Furthermore, with strong atomic-level oxygen absorption into its subsurface, ultrasmall Pt catalytically serves as the nucleation site for Li2O2 growth. The Li2O2 is subsequently induced into a favorable form with small size and amorphous state, decomposed more easily during recharge. Meanwhile, the conductive hollow graphene substrate can enhance the catalytic activity of noble metal Pt catalysts due to the graphene-metal interfacial interaction. Benefiting from the above synergistic effects between the hollow graphene nanocages and the nanosized Pt catalysts, the ultrasmall Pt-decorated graphene nanocage cathode exhibits enhanced electrochemical performances.

Kinetic Study of Parasitic Reactions in Lithium-Ion Batteries: A Case Study on LiNi0.6Mn0.2Co0.2O2

Abstract: The side reactions between the electrode materials and the nonaqueous electrolytes have been the major contributor to the degradation of electrochemical performance of lithium-ion batteries. A home-built high-precision leakage current measuring system was deployed to investigate the reaction kinetics between the delithiated LiNi(0.6)Mn(0.2)Co(0.2)O2 and a conventional nonaqueous electrolyte. It was found that the rate of parasitic reaction had strong dependence on the upper cutoff potential of the cathode material. The kinetic data also indicated a change of reaction mode at about 4.5 V vs Li(+)/Li.

Ultrafast and Highly Reversible Sodium Storage in Zinc-Antimony Intermetallic Nanomaterials

Abstract: The progress on sodium-ion battery technology faces many grand challenges, one of which is the considerably lower rate of sodium insertion/deinsertion in electrode materials due to the larger size of sodium (Na) ions and complicated redox reactions compared to the lithium-ion systems. Here, it is demonstrated that sodium ions can be reversibly stored in Zn-Sb intermetallic nanowires at speeds that can exceed 295 nm s-1. Remarkably, these values are one to three orders of magnitude higher than the sodiation rate of other nanowires electrochemically tested with in situ transmission electron micro­scopy. It is found that the nanowires display about 161% volume expansion after the first sodiation and then cycle with an 83% reversible volume expansion. Despite their massive expansion, the nanowires can be cycled without any cracking or facture during the ultrafast sodiation/desodiation process. Additionally, most of the phases involved in the sodiation/desodiation process possess high electrical conductivity. More specifically, the NaZnSb exhibits a layered structure, which provides channels for fast Na+ diffusion. This observation indicates that Zn-Sb intermetallic nanomaterials offer great promise as high rate and good cycling stability anodic materials for the next generation of sodium-ion batteries.

Nigrostriatal Dopamine Acting on Globus Pallidus Regulates Sleep

Abstract: Lesions of the globus pallidus externa (GPe) produce a profound sleep loss (∼45%) in rats, suggesting that GPe neurons promote sleep. As GPe neuronal activity is enhanced by dopamine (DA) from the substantia nigra pars compacta (SNc), we hypothesized that SNc DAviathe GPe promotes sleep. To test this hypothesis, we selectively destroyed the DA afferentsto the caudoputamen (CPu) using 6-hydroxydopamine and examined changes in sleep-wake profiles in rats. Rats with 80–90% loss of SNc neurons displayed a significant 33.7% increase in wakefulness (or sleep reduction). This increase significantly correlated with the extent of SNc DA neuron loss. Furthermore, these animals exhibited sleep-wake fragmentation and reduced diurnal variability of sleep.We then optogenetic-stimulated SNc DA terminalsin the CPuand foundthat 20-Hzstimulation from 9 to 10 PM increased total sleep by 69% with high electroencephalograph (EEG) delta power. We finally directly optogenetic-stimulated GPe neurons and found that 20-Hz stimulation of the GPe from 9 to 10 PM increased total sleep by 66% and significantly increased EEG delta power. These findings elucidate a novel circuit for DA control of sleep and the mechanisms of abnormal sleep in BG disorders such as Parkinson’s disease and Huntington’s disease.

Atomic Layer Deposition for Lithium‐Based Batteries

Abstract: With the increasing demand for energy at a low cost and minimal environmental impact, the development of next-generation high-performance batteries has drawn considerable attention. Owing to the capability of forming conformal coatings of thin films and nanoparticles, atomic layer deposition (ALD) has shown great potential in deposition and surface modification of electrode materials with various nanostructures, deposition of solid-state electrolyte, and fabrication of electrochemical catalysts. This paper reviews the recent development and applications of ALD in Li-based batteries, especially beyond Li-ion systems, and provides suggestions for further development of ALD techniques for these batteries.

New Insights into the Instability of Discharge Products in Na–O2 Batteries

Abstract: Sodium–oxygen batteries currently stimulate extensive research due to their high theoretical energy density and improved operational stability when compared to lithium–oxygen batteries. Cell stability, however, needs to be demonstrated also under resting conditions before future implementation of these batteries. In this work we analyze the effect of resting periods on the stability of the sodium superoxide (NaO2) discharge product. The instability of NaO2 in the cell environment is demonstrated leading to the evolution of oxygen during the resting period and the decrease of the cell efficiency. In addition, migration of the superoxide anion (O2–) in the electrolyte is observed and demonstrated to be an important factor affecting Coulombic efficiency.

Ultrasonic-assisted pyrolyzation fabrication of reduced SnO2–x /g-C3N4 heterojunctions: Enhance photoelectrochemical and photocatalytic activity under visible LED light irradiation

Abstract: Novel SnO2–x /g-C3N4 heterojunction nanocomposites composed of reduced SnO2–x nanoparticles and exfoliated g-C3N4 nanosheets were prepared by a convenient one-step pyrolysis method. The structural, morphological, and optical properties of the as-prepared nanocomposites were characterized in detail, indicating that the aggregation of g-C3N4 nanosheets was prevented by small, well-dispersed SnO2–x nanoparticles. The ultraviolet–visible spectroscopy absorption bands of the nanocomposites were shifted to a longer wavelength region than those exhibited by pure SnO2 or g-C3N4. The charge transfer and recombination processes occurring in the nanocomposites were investigated using linear scan voltammetry and electrochemical impedance spectroscopy. Under 30-W visible-light-emitting diode irradiation, the heterojunction containing 27.4 wt.% SnO2–x exhibited the highest photocurrent density of 0.0468 mA·cm–2, which is 33.43 and 5.64 times larger than that of pure SnO2 and g-C3N4, respectively. The photocatalytic activity of the heterojunction material was investigated by degrading rhodamine B under irradiation from the same light source. Kinetic study revealed a promising degradation rate constant of 0.0226 min−1 for the heterojunction containing 27.4 wt.% SnO2–x , which is 32.28 and 5.79 times higher than that of pure SnO2 and g-C3N4, respectively. The enhanced photoelectrochemical and photocatalytic performances of the nanocomposite may be due to its appropriate SnO2–x content and the compact structure of the junction between the SnO2–x nanoparticles and the g-C3N4 nanosheets, which inhibits the recombination of photogenerated electrons and holes.

Prodrug strategies for paclitaxel

Abstract: Paclitaxel is an anti-tumor agent with remarkable anti-tumor activity and wide clinical uses. However, it is also faced with various challenges especially for its poor water solubility and low selectivity for the target. To overcome these disadvantages of paclitaxel, approaches using small molecule modifications and macromolecule modifications have been developed by many research groups from all over the world. In this review, we discuss the different strategies especially prodrug strategies that are currently used to make paclitaxel more effective.