Hong-Jie Yang

Alkanethiol-Passivated Ge Nanowires as High-Performance Anode Materials for Lithium-Ion Batteries: The Role of Chemical Surface Functionalization

We demonstrate that dodecanethiol monolayer passivation can significantly enhance the anode performance of germanium (Ge) nanowires in lithium-ion batteries. The dodecanethiol-passivated Ge nanowires exhibit an excellent electrochemical performance with a reversible specific capacity of 1130 mAh/g at 0.1 C rate after 100 cycles. The functionalized Ge nanowires show high-rate capability having charge and discharge capacities of ∼555 mAh/g at high rates of 11 C. The functionalized Ge nanowires also performed well at 55 °C, showing their thermal stability at high working temperatures. Moreover, full cells using a LiFePO(4) cathode were assembled and the electrodes still have stable capacity retention. An aluminum pouch type lithium cell was also assembled to provide larger current (∼30 mA) for uses on light-emitting-diodes (LEDs) and audio devices. Investigation of the role of organic monolayer coating showed that the wires formed a robust nanowire/PVDF network through strong C-F bonding so as to maintain structure integrity during the lithiation/delithiation process. Organic monolayer-coated Ge nanowires represent promising Ge-C anodes with controllable low carbon content (ca. 2-3 wt %) for high capacity, high-rate lithium-ion batteries and are readily compatible with the commercial slurry-coating process for cell fabrication.

Simultaneous induction of autophagy and toll-like receptor signaling pathways by graphene oxide

Graphene oxide (GO) nanosheets have sparked growing interests in biological and medical applications. This study examined how macrophage, the primary immune cell type engaging microbes, responded to GO treatment. We uncovered that incubation of macrophage cell RAW264.7 with GO elicited autophagy in a concentration-dependent manner, as evidenced by the appearance of autophagic vacuoles and activation of autophagic marker proteins. Such GO-induced autophagy was observed in various cell lines and in macrophage treated with GO of different sizes. Strikingly, GO treatment of macrophage provoked the toll-like receptor (TLR) signaling cascades and triggered ensuing cytokine responses. Molecular analysis identified that TLR4 and TLR9 and their downstream signaling mediators MyD88, TRAF6 and NF-κB played pivotal roles in the GO-induced inflammatory responses. By silencing individual genes in the signaling pathway, we further unveiled that the GO-induced autophagy was modulated by TLR4, TLR9 and was dependent on downstream adaptor proteins MyD88, TRIF and TRAF6. Altogether, we demonstrated that GO treatment of cells simultaneously triggers autophagy and TLR4/TLR9-regulated inflammatory responses, and the autophagy was at least partly regulated by the TLRs pathway. This study thus suggests a mechanism by which cells respond to nanomaterials and underscores the importance of future safety evaluation of nanomaterials.

Self-seeded growth of five-fold twinned copper nanowires: mechanistic study, characterization, and SERS applications.

A comprehensive mechanistic study conducted on the formation mechanism of five-fold twinned copper nanowires by heating copper(I) chloride with oleylamine at 170 °C is presented. Electron microscopy and UV-visible absorption spectra are used to analyze the growth mechanism of copper nanowires. High-resolution transmission electron microscopy and selected-area electron diffraction are used to investigate the detailed structure of copper nanowires and nanoparticles, and a five-twinned structure is shown to exist in the copper nanowires and nanoparticles. Additionally, experiments have been performed to indirectly confirm that oleylamine preferentially adsorbs on the {100} facets of growing crystals. On the basis of the above results, the self-seeded growth of copper nanowires is confirmed. In the initial stage of reactions, copper nanoparticles with two distinctive sizes are formed. As the reaction proceeds, larger five-twinned copper nanoparticles serve as seeds for anisotropic crystal growth. Further, copper atoms generated from an Ostwald ripening process or reduction reactions of a copper(I) chloride-oleylamine complex continue to deposit and crystallize on the twin boundaries. Once the {110} planes are generated, oleylamine preferentially adsorbs on the newly formed {100} facets and then guides the formation of nanowires. The electrical resistivity of a single copper nanowire is measured to be 41.25 nΩ-m, which is of the same order of magnitude as the value of bulk copper (16.78 nΩ-m). Finally, an effective surface-enhanced Raman spectroscopy active substrate made of copper nanowire is used to detect the 4-mercaptobenzoic acid molecules.

Graphene Oxide Triggers Toll‐Like Receptors/Autophagy Responses In Vitro and Inhibits Tumor Growth In Vivo

Graphene oxide (GO) is a nanomaterial with burgeoning bioapplications, while autophagy is implicated in cancer therapy. Although induction of autophagy by nanomaterials is reported, the underlying signaling mechanism in cancer cells and how this implicates the potential of GO in cancer therapy remain obscure. Here, it is shown that GO itself can induce the toll-like receptors (TLRs) responses and autophagy in cancer cells and confer antitumor effects in mice. GO can be phagocytosed by CT26 colon cancer cells, simultaneously triggering autophagy as well as TLR-4 and TLR-9 signaling cascades. By dissecting the crosstalk between the TLRs and autophagy pathways, it is uncovered that the GO-activated autophagy is regulated through the myeloid differentiation primary response gene 88 (MyD88)- and TNF receptor-associated factor 6 (TRAF6)-associated TLR-4/9 signaling pathways. Injection of GO alone into immunocompetent mice bearing the CT26 colon tumors not only suppresses the tumor progression but also enhances cell death, autophagy, and immune responses within the tumor bed. These data altogether implicate the potential of GO as an effective nanomaterial for autophagy induction and cancer therapy.

Ferromagnetic germanide in Ge nanowire transistors for spintronics application.

To explore spintronics applications for Ge nanowire heterostructures formed by thermal annealing, it is critical to develop a ferromagnetic germanide with high Curie temperature and take advantage of the high-quality interface between Ge and the formed ferromagnetic germanide. In this work, we report, for the first time, the formation and characterization of Mn(5)Ge(3)/Ge/Mn(5)Ge(3) nanowire transistors, in which the room-temperature ferromagnetic germanide was found through the solid-state reaction between a single-crystalline Ge nanowire and Mn contact pads upon thermal annealing. The atomically clean interface between Mn(5)Ge(3) and Ge with a relatively small lattice mismatch of 10.6% indicates that Mn(5)Ge(3) is a high-quality ferromagnetic contact to Ge. Temperature-dependent I-V measurements on the Mn(5)Ge(3)/Ge/Mn(5)Ge(3) nanowire heterostructure reveal a Schottky barrier height of 0.25 eV for the Mn(5)Ge(3) contact to p-type Ge. The Ge nanowire field-effect transistors built on the Mn(5)Ge(3)/Ge/Mn(5)Ge(3) heterostructure exhibit a high-performance p-type behavior with a current on/off ratio close to 10(5), and a hole mobility of 150-200 cm(2)/(V s). Temperature-dependent resistance of a fully germanided Mn(5)Ge(3) nanowire shows a clear transition behavior near the Curie temperature of Mn(5)Ge(3) at about 300 K. Our findings of the high-quality room-temperature ferromagnetic Mn(5)Ge(3) contact represent a promising step toward electrical spin injection into Ge nanowires and thus the realization of high-efficiency spintronic devices for room-temperature applications.

Electrical spin injection and detection in Mn5Ge3/Ge/Mn5Ge3 nanowire transistors.

In this Letter, we report the electrical spin injection and detection in Ge nanowire transistors with single-crystalline ferromagnetic Mn5Ge3 as source/drain contacts formed by thermal reactions. Degenerate indium dopants were successfully incorporated into as-grown Ge nanowires as p-type doping to alleviate the conductivity mismatch between Ge and Mn5Ge3. The magnetoresistance (MR) of the Mn5Ge3/Ge/Mn5Ge3 nanowire transistor was found to be largely affected by the applied bias. Specifically, negative and hysteretic MR curves were observed under a large current bias in the temperature range from T = 2 K up to T = 50 K, which clearly indicated the electrical spin injection from ferromagnetic Mn5Ge3 contacts into Ge nanowires. In addition to the bias effect, the MR amplitude was found to exponentially decay with the Ge nanowire channel length; this fact was explained by the dominated Elliot-Yafet spin-relaxation mechanism. The fitting of MR further revealed a spin diffusion length of lsf = 480 ± 13 nm and a spin lifetime exceeding 244 ps at T = 10 K in p-type Ge nanowires, and they showed a weak temperature dependence between 2 and 50 K. Ge nanowires showed a significant enhancement in the measured spin diffusion length and spin lifetime compared with those reported for bulk p-type Ge. Our study of the spin transport in the Mn5Ge3/Ge/Mn5Ge3 nanowire transistor points to a possible realization of spin-based transistors; it may also open up new opportunities to create novel Ge nanowire-based spintronic devices. Furthermore, the simple fabrication process promises a compatible integration into standard Si technology in the future.

Single-crystalline Ni2Ge/Ge/Ni2Ge nanowire heterostructure transistors

In this study, we report on the formation of a single-crystalline Ni(2)Ge/Ge/Ni(2)Ge nanowire heterostructure and its field effect characteristics by controlled reaction between a supercritical fluid-liquid-solid (SFLS) synthesized Ge nanowire and Ni metal contacts. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal a wide temperature range to convert the Ge nanowire to single-crystalline Ni(2)Ge by a thermal diffusion process. The maximum current density of the fully germanide Ni(2)Ge nanowires exceeds 3.5 × 10(7) A cm(-2), and the resistivity is about 88 μΩ cm. The in situ reaction examined by TEM shows atomically sharp interfaces for the Ni(2)Ge/Ge/Ni(2)Ge heterostructure. The interface epitaxial relationships are determined to be [Formula: see text] and [Formula: see text]. Back-gate field effect transistors (FETs) were also fabricated using this low resistivity Ni(2)Ge as source/drain contacts. Electrical measurements show a good p-type FET behavior with an on/off ratio over 10(3) and a one order of magnitude improvement in hole mobility from that of SFLS-synthesized Ge nanowire.

Graphene oxide as a chemosensitizer: Diverted autophagic flux, enhanced nuclear import, elevated necrosis and improved antitumor effects

Graphene oxide (GO) is a nanomaterial that provokes autophagy in CT26 colon cancer cells and confers antitumor effects. Here we demonstrated that both GO and the chemotherapy drug cisplatin (CDDP) induced autophagy but elicited low degrees of CT26 cell death. Strikingly, GO combined with CDDP (GO/CDDP) potentiated the CT26 cell killing via necrosis. GO/CDDP not only elicited autophagy, but induced the nuclear import of CDDP and the autophagy marker LC3. The nuclear LC3 did not co-localize with p62 or Lamp-2, neither did blocking autolysosome formation significantly hinder the nuclear import of LC3/CDDP and necrosis, indicating that autophagosome and autolysosome formation was dispensable. Conversely, suppressing phagophore formation and importin-α/β significantly alleviated the nuclear import of LC3/CDDP and necrosis. These data suggested that GO/CDDP diverted the LC3 flux in the early phase of autophagy, resulting in LC3 trafficking towards the nucleus in an importin-α/β-dependent manner, which concurred with the CDDP nuclear import and necrosis. Intratumoral injection of GO/CDDP into mice bearing CT26 colon tumors potentiated immune cell infiltration and promoted cell death, autophagy and HMGB1 release, thereby synergistically augmenting the antitumor effects. Altogether, we unveiled a mechanism concerning how nanomaterials chemosensitize cancer cells and demonstrated the potentials of GO as a chemosensitizer.

High-yield, high-throughput synthesis of germanium nanowires by metal–organic chemical vapor deposition and their functionalization and applications

In this study, a direct liquid-injection metal–organic chemical vapor deposition (LIMOCVD) is developed as a novel synthetic method for high-yield, large-scale synthesis of Ge nanowiresvia vapor–liquid–solid (VLS) growth at temperatures ranging from 390 to 480 °C at atmospheric pressure. Among the precursors tested, including diphenylgermane (DPG), n-butylgermane (NBG), and tetraethylgermane (TEG), DPG exhibited the most suitable reactivity for LIMOCVD nanowire reactions. While using DPG as a precursor, the yields of Ge nanowires by VLS growth can reach up to ∼30%. As a proof-of-concept for scale-up synthesis, sub-gram quantities of Ge nanowires were produced by consecutive injections of precursor solution. The Ge wires were passivated by an alkanethiol monolayer which gives rise to stability, oxidation resistance and significantly improved dispersibility in organic solvents. Nanowire solutions could be used as inks for applications in many fields. For example, bendable, thickness-tunable Ge nanowire fabrics were fabricated from the inks. The LIMOCVD-VLS growth could potentially serve as a facile and reliable method for industrial-scale production of Ge nanowires due to its superior synthetic capacity and low manufacturing cost.

Seeded silicon nanowire growth catalyzed by commercially available bulk metals: broad selection of metal catalysts, superior field emission performance, and versatile nanowire/metal architectures

Over the past two decades, metal-seeded growth has been the most widely used method for Si nanowire synthesis. However, preparation methods of metal catalysts mostly involve indirect, multi-step procedures and suffer from many processing limitations. In this study, we demonstrate that bulk metals can be directly used as catalysts for seeded Si nanowire growth. Eight metals which cover all three types of metals used for Si nanowire growth, such as Ag, Al, Au, Cu, Fe, Ni, Pb and Ti, were explored as catalysts. Single crystalline Si nanowires were synthesized in the presence of bulk Ag, Al, Cu, Fe, Ni, Pb, and Ti at temperatures ranging from 450 to 550 °C at 10.3 MPa, whereas no wires were produced in the presence of bulk Au. The metals effective for seeded growth are cheap, easily obtained, and exhibit excellent catalytic reusability. In addition, as-grown Si nanowires exhibit superior field emission property due to their good electrical contact between the wire and metal interface. Various nanowire/metal substrate architectures could be achieved through the use of metals with different morphologies. Compared to the traditional seeded-growth protocol, bulk metal-catalyzed growth provides a more facile and flexible synthetic scheme and a direct route to grow Si nanowires on metal substrates for advanced nanowire applications.