Hsing-Yu Tuan

Ultrathin gold nanowires can be obtained by reducing polymeric strands of oleylamine-AuCl complexes formed via aurophilic interaction.

This Communication describes a facile route to the preparation of ultrathin gold nanowires using linear chains formed from [(oleylamine)AuCl] complex via aurophilic interaction. The linear chains, with AuI...AuI bonds as the backbone and surrounded by oleylamines, can group together to form bundles of polymeric strands. When the AuI was reduced to Au0 by reacting with Ag nanoparticles in hexane, the polymeric strands functioned as both the source of Au and the template to mediate the nucleation and growth of Au nanowires. Using this method, we were able to produce Au nanowires with an average diameter of approximately 1.8 nm and an aspect ratio of >1000 in high yields (approximately 70%).

A graphene-based platform for induced pluripotent stem cells culture and differentiation.

Induced pluripotent stem cells (iPSCs) hold great promise as a cell source for regenerative medicine yet its culture, maintenance of pluripotency and induction of differentiation remain challenging. Conversely, graphene (G) and graphene oxide (GO) have captured tremendous interests in the fields of materials science, physics, chemistry and nanotechnology. Here we report on that G and GO can support the mouse iPSCs culture and allow for spontaneous differentiation. Intriguingly, G and GO surfaces led to distinct cell proliferation and differentiation characteristics. In comparison with the glass surface, iPSCs cultured on the G surface exhibited similar degrees of cell adhesion and proliferation while iPSCs on the GO surface adhered and proliferated at a faster rate. Moreover, G favorably maintained the iPSCs in the undifferentiated state while GO expedited the differentiation. The iPSCs cultured on both G and GO surfaces spontaneously differentiated into ectodermal and mesodermal lineages without significant disparity, but G suppressed the iPSCs differentiation towards the endodermal lineage whereas GO augmented the endodermal differentiation. These data collectively demonstrated that the different surface properties of G and GO governed the iPSCs behavior and implicate the potentials of graphene-based materials as a platform for iPSCs culture and diverse applications.

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.

Solution−Liquid−Solid (SLS) Growth of Silicon Nanowires

Here we report the solution-liquid-solid (SLS) synthesis of silicon (Si) nanowires. Nanowires are grown by trisilane (Si3H8) decomposition in a high boiling solvent, octacosane (C28H58) or squalane (C30H62), in the presence of either Au or Bi nanocrystals. To our knowledge, this is the first report of a colloidal synthetic route carried out in a solvent at atmospheric pressure that provides crystalline Si nanowires in large quantities.

Gram-Scale Synthesis of Catalytic Co9S8 Nanocrystal Ink as a Cathode Material for Spray-Deposited, Large-Area Dye-Sensitized Solar Cells

We report the development of Co9S8 nanocrystals as a cost-effective cathode material that can be readily combined with spraying techniques to fabricate large-area dye-sensitized solar cell (DSSC) devices and can be further connected with series or parallel cell architectures to obtain a relatively high output voltage or current. A gram-scale synthesis of Co9S8 nanocrystal is carried out via a noninjection reaction by mixing anhydrous CoCl2 with trioctylphosphine (TOP), dodecanethiol and oleylamine (OLA) at 250 °C. The Co9S8 nanocrystals possess excellent catalytic ability with respect to I(-)/I3(-) redox reactions. The Co9S8 nanocrystals are prepared as nanoinks to fabricate uniform, crack-free Co9S8 thin films on different substrates by using a spray deposition technique. These Co9S8 films are used as counter electrodes assembled with dye-adsorbed TiO2 photoanodes to fabricate DSSC devices having a working area of 2 cm(2) and an average power conversion efficiency (PCE) of 7.02 ± 0.18% under AM 1.5 solar illumination, which is comparable with the PCE of 7.2 ± 0.12% obtained using a Pt cathode. Furthermore, six 2 cm(2)-sized DSSC devices connected in series output an open-circuit voltage of 4.2 V that can power a wide range of electronic devices such as LED arrays and can charge commercial lithium ion batteries.

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.

Solvothermal Synthesis of Zincblende and Wurtzite CuInS2 Nanocrystals and Their Photovoltaic Application

We report a simple solvothermal synthesis approach to the growth of CuInS(2) nanocrystals with zincblende- and wurtzite-phase structures. Zincblende nanocrystals with particle sizes of 10-20 nm were produced using oleylamine as the solvent. When ethylenediamine was used as the solvent, similarly sized wurtzite nanocrystals with some degree of particle aggregation were formed. Use of a mixture of these solvents gave products with mixed phases including some polyhedral nanostructures. The crystal phases of these nanocrystals were carefully determined by X-ray diffraction and transmission electron microscopy analysis. All the samples exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1300 nm. Pure-phase zincblende and wurtzite CuInS(2) nanocrystals were employed as ink in the fabrication of solar cells. The spray-coated nanocrystal layer was subjected to a selenization process. A power conversion efficiency of ~0.74% and a good external quantum efficiency profile over broad wavelengths have been measured. The results demonstrate that wurtzite and zincblende CuInS(2) nanocrystals may be attractive precursors to light-absorbing materials for making efficient photovoltaic devices.

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.

Facile colloidal synthesis of quinary CuIn1−xGax(SySe1−y)2 (CIGSSe) nanocrystal inks with tunable band gaps for use in low-cost photovoltaics

We report, for the first time, colloidal synthesis of quinary CuIn1−xGax(SySe1−y)2 (CIGSSe) nanocrystals across the entire composition range (x,y) = 0 to 1 with band gaps tunable in the range of 0.98 to 2.40 eV by facile chemical synthesis. As a proof-of-concept, thin-film solar cells made by using the CIGSSe nanocrystal inks as an absorber layer precursor exhibited an efficiency over 1% under AM 1.5 illumination.