Thermally Driven Structural Order of Oligo(Ethylene Glycol)-Terminated Alkanethiol Monolayers on Au(111) Prepared by Vapor Deposition.

To probe the effects of deposition temperature on the formation and structural order of self-assembled monolayers (SAMs) on Au(111) prepared by vapor deposition of 2-(2-methoxyethoxy)ethanethiol (CH3O(CH2)2O(CH2)2SH, EG2) for 24 h, we examined the surface structure and electrochemical behavior of the resulting EG2 SAMs using scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM observations clearly revealed that EG2 SAMs vapor-deposited on Au(111) at 298 K were composed of a disordered phase on the entire Au surface, whereas those formed at 323 K showed improved structural order, showing a mixed phase of ordered and disordered phases. Moreover, at 348 K, uniform and highly ordered EG2 SAMs on Au(111) were formed with a (2 × 3√3) packing structure. CV measurements showed sharp reductive desorption (RD) peaks at -0.818, -0.861, and -0.880 V for EG2 SAM-modified Au electrodes formed at 298, 323, and 348 K, respectively. More negative potential shifts of RD peaks with increasing deposition temperature are attributed to an increase in van der Waals interactions between EG2 molecular backbones resulting from the improved structural quality of EG2 SAMs. Our results obtained herein provide new insights into the formation and thermally driven structural order of oligo(ethylene glycol)-terminated SAMs vapor-deposited on Au(111).

Urine IP-10 as a biomarker of therapeutic response in patients with active pulmonary tuberculosis.

BACKGROUND: Prior to clinical trials of new TB drugs or therapeutic vaccines, it is necessary to develop monitoring tools to predict treatment outcomes in TB patients. Urine interferon gamma inducible protein 10 (IP-10) is a potential biomarker of treatment response in chronic hepatitis C virus infection and lung diseases, including tuberculosis. In this study, we assessed IP-10 levels in urine samples from patients with active TB at diagnosis, during treatment, and at completion, and compared these with levels in serum samples collected in parallel from matched patients to determine whether urine IP-10 can be used to monitor treatment response in patients with active TB. METHODS: IP-10 was measured using enzyme-linked immunosorbent assays in urine and serum samples collected concomitantly from 23 patients with active TB and 21 healthy adults (44 total individuals). The Mann-Whitney U test and Wilcoxon matched-pairs signed rank test were used for comparisons among healthy controls and patients at three time points, and LOESS regression was used for longitudinal data. RESULTS: The levels of IP-10 in urine increased significantly after 2 months of treatment (P = 0.0163), but decreased by the completion of treatment (P = 0.0035). Serum IP-10 levels exhibited a similar trend, but did not increase significantly after 2 months of treatment in patients with active TB. CONCLUSIONS: Unstimulated IP-10 in urine can be used as a biomarker to monitor treatment response in patients with active pulmonary TB.

Ordered Mesoporous C3 N5 with a Combined Triazole and Triazine Framework and Its Graphene Hybrids for the Oxygen Reduction Reaction (ORR).

Mesoporous carbon nitrides (MCN) with C3 N4 stoichiometry could find applications in fields ranging from catalysis, sensing, and adsorption-separation to biotechnology. The extension of the synthesis of MCN with different nitrogen contents and chemical structures promises access to a wider range of applications. Herein we prepare mesoporous C3 N5 with a combined triazole and triazine framework via a simple self-assembly of 5-amino-1H-tetrazole (5-ATTZ). We are able to hybridize these nanostructures with graphene by using graphene-mesoporous-silica hybrids as a template to tune the electronic properties. DFT calculations and spectroscopic analyses clearly demonstrate that the C3 N5 consists of 1 triazole and 2 triazine moieties. The triazole-based mesoporous C3 N5 and its graphene hybrids are found to be highly active for oxygen reduction reaction (ORR) with a higher diffusion-limiting current density and a decreased overpotential than those of bulk g-C3 N4 .

A 2D Metal Oxide Nanosheet as an Efficient Additive for Improving Na-Ion Electrode Activity of Graphene-Based Nanocomposites.

An efficient way to improve the Na-ion electrode activity of graphene-based nanocomposite is developed by employing exfoliated metal oxide nanosheet as an additive. The titanate-nanosheet-incorporated Na-SnS2 -reduced graphene oxide (rG-O) nanocomposites can be synthesized by the electrostatically derived restacking of the colloidal mixture of SnS2 , rG-O, and titanate nanosheets with the Na+ cation. The incorporation of titanate into the Na-SnS2 -rG-O nanocomposites is effective in improving the nanoscale mixing of component nanosheets and the porosity of the composite structure. The resulting nanocomposites deliver superior discharge capacities and rate properties to the titanate-free nanocomposite. The universal applicability is further confirmed by MoS2 -rG-O nanocomposites upon the addition of titanate. This study highlights that the exfoliated metal oxide nanosheet can be used as an efficient additive for graphene-based nanocomposites to explore Na-ion electrode materials.

A Conductive Hybridization Matrix of RuO2 Two-Dimensional Nanosheets: A Hybrid-Type Photocatalyst.

A universal methodology to efficiently improve the photocatalyst performance of semiconductors was developed by employing exfoliated RuO2 two-dimensional nanosheets as a conducting hybridization matrix. The hybridization with a RuO2 nanosheet is easily achieved by crystal growth or electrostatically derived anchoring of semiconductor nanocrystals on the RuO2 nanosheet. An enhanced chemical interaction of inorganic semiconductor with hydrophilic RuO2 nanosheet is fairly effective in optimizing their photocatalytic activity and photostability by the enhancement of charge separation and charge mobility. The RuO2 -containing nanohybrids show much better photocatalyst functionalities than do the graphene-containing ones. The present study clearly demonstrates that hydrophilic RuO2 nanosheets are superior hybridization matrices, over the widely used hydrophobic graphene nanosheets, for exploring new efficient hybrid-type photocatalysts.

Highly Durable and Active PtFe Nanocatalyst for Electrochemical Oxygen Reduction Reaction.

Demand on the practical synthetic approach to the high performance electrocatalyst is rapidly increasing for fuel cell commercialization. Here we present a synthesis of highly durable and active intermetallic ordered face-centered tetragonal (fct)-PtFe nanoparticles (NPs) coated with a "dual purpose" N-doped carbon shell. Ordered fct-PtFe NPs with the size of only a few nanometers are obtained by thermal annealing of polydopamine-coated PtFe NPs, and the N-doped carbon shell that is in situ formed from dopamine coating could effectively prevent the coalescence of NPs. This carbon shell also protects the NPs from detachment and agglomeration as well as dissolution throughout the harsh fuel cell operating conditions. By controlling the thickness of the shell below 1 nm, we achieved excellent protection of the NPs as well as high catalytic activity, as the thin carbon shell is highly permeable for the reactant molecules. Our ordered fct-PtFe/C nanocatalyst coated with an N-doped carbon shell shows 11.4 times-higher mass activity and 10.5 times-higher specific activity than commercial Pt/C catalyst. Moreover, we accomplished the long-term stability in membrane electrode assembly (MEA) for 100 h without significant activity loss. From in situ XANES, EDS, and first-principles calculations, we confirmed that an ordered fct-PtFe structure is critical for the long-term stability of our nanocatalyst. This strategy utilizing an N-doped carbon shell for obtaining a small ordered-fct PtFe nanocatalyst as well as protecting the catalyst during fuel cell cycling is expected to open a new simple and effective route for the commercialization of fuel cells.

Porous Hybrid Network of Graphene and Metal Oxide Nanosheets as Useful Matrix for Improving the Electrode Performance of Layered Double Hydroxides.

Mesoporous hybrid network of reduced graphene oxide (rG-O) and layered MnO(2) nanosheets could act as an efficient immobilization matrix for improving the electrochemical activity of layered double hydroxide (LDH). The control of MnO(2) /rG-O ratio is crucial in optimizing the porous structure and electrical conductivity of the resulting hybrid structure. The immobilization of Co-Al-LDH on hybrid MnO(2) /rG-O network is more effective in enhancing its electrode activity compared with that of on pure rG-O network. The Co-Al-LDH-rG-O-MnO(2) nanohybrid deliveres a greater specific capacitance than does MnO(2) -free Co-Al-LDH-rG-O nanohybrid. The beneficial effect of MnO(2) incorporation on the electrode performance of nanohybrid is more prominent for higher current density and faster scan rate, underscoring the significant enhancement of the electron transport of Co-Al-LDH-rG-O. This is supported by electrochemical impedance spectroscopy. The present study clearly demonstrates the usefulness of the porously assembled hybrid network of graphene and metal oxide nanosheets as an effective platform for exploring efficient LDH-based functional materials.

RuO2-ReO3 composite nanofibers for efficient electrocatalytic responses.

We present a facile synthetic route to ruthenium dioxide (RuO2)-rhenium oxide (ReO3) electrospun composite nanofibers and their electrocatalytic responses for capacitance and H2O2 sensing. The contents of rhenium oxide of electrospun ruthenium dioxide (RuO2) were carefully controlled by an electrospinning process with the preparation of the precursor solutions followed by the thermal annealing process in air. The electrochemical applications of RuO2-ReO3 electrospun composite nanofibers were then investigated by modifying these materials on the surface of glassy carbon (GC) electrodes, RuO2-ReO3(n)/GC (n = 0.0, 0.07, 0.11, and 0.13), where n denotes the relative atomic ratio of Re to the sum of Ru and Re. Specific capacitance and H2O2 reduction sensitivity were remarkably enhanced depending on the amount of ReO3 increased. Among the four compositions of RuO2-ReO3(n), RuO2-ReO3(0.11)/GC showed the highest performances, i.e., a 20.9-fold higher specific capacitance (205 F g(-1) at a potential scan rate (v) of 10 mV s(-1); a capacity loss of 19% from v = 10 to 2000 mV s(-1)) and a 7.6-fold higher H2O2 reduction sensitivity (668 µA mM(-1) cm(-2), normalized by GC disk area), respectively, compared to only RuO2/GC.

Ruthenium based nanostructures driven by morphological controls as efficient counter electrodes for dye-sensitized solar cells.

We introduce a facile approach to use ruthenium dioxide (RuO2) and ruthenium (Ru) nanostructures as effective counter electrodes instead of using platinum (Pt) for dye-sensitized solar cells (DSSCs). RuO2 and Ru nanostructure layers on the FTO glass can be readily prepared by a simple annealing process followed by the spin coating process of the mixture solution containing amorphous RuO2·xH2O precursor and poly(ethylene oxide) (PEO) as a dispersion matrix at low temperature in air. The Ru metal nanostructure layer prepared by the reduction of RuO2 with H2 shows the highest efficiency of 6.77% in DSSC operation, which is comparable to the efficiency of the Pt electrode (7.87%).

Composition-tailored 2 D Mn(1-x)Ru(x)O(2) nanosheets and their reassembled nanocomposites: improvement of electrode performance upon Ru substitution.

Composition-tailored Mn1-x Rux O2 2 D nanosheets and their reassembled nanocomposites with mesoporous stacking structure are synthesized by a soft-chemical exfoliation reaction and the subsequent reassembling of the exfoliated nanosheets with Li(+) cations, respectively. The tailoring of the chemical compositions of the exfoliated Mn1-x Rux O2 2 D nanosheets and their lithiated nanocomposites can be achieved by adopting the Ru-substituted layered manganese oxides as host materials for exfoliation reaction. Upon the exfoliation-reassembling process, the substituted ruthenium ions remain stabilized in the layered Mn1-x Rux O2 lattice with mixed Ru(3+) /Ru(4+) oxidation state. The reassembled Li-Mn1-x Rux O2 nanocomposites show promising pseudocapacitance performance with large specific capacitances of approximately 330 F g(-1) for the second cycle and approximately 360 F g(-1) for the 500th cycle and excellent cyclability, which are superior to those of the unsubstituted Li-MnO2 homologue and many other MnO2 -based materials. Electrochemical impedance spectroscopy analysis provides strong evidence for the enhancement of the electrical conductivity of 2 D nanostructured manganese oxide upon Ru substitution, which is mainly responsible for the excellent electrode performance of Li-Mn1-x Rux O2 nanocomposites. The results underscore the powerful role of the composition-controllable metal oxide 2 D nanosheets as building blocks for exploring efficient electrode materials.

Unique properties of 2 D layered titanate nanosheets as a building block for the optimization of the photocatalytic activity and photostability of TiO2-based nanohybrids.

In comparison with the hybridization with 0D TiO2 nanoparticle, 2D layered TiO2 nanosheets are much more effective in the improvement of the photocatalytic activity and photostability of semiconducting compounds. The 2D TiO2-Ag3PO4 nanohybrid described in this paper shows a greater decrease in the electron-hole recombination upon hybridization and a stronger chemical interaction between the components than the 0D homologue. This result confirms the benefits of 2D layered TiO2 nanosheets as a building block for efficient hybrid-type photocatalyst materials.

Electrical characterization of organic monolayers at a nanoscale.

This study investigates the electrical properties of viologen derivatives at a nanoscale and analyzes it using a scanning tunneling microscopy (STM) in order to apply viologen molecules that represent a function in electron transfer mediators as a molecular electronic device. In addition, we measure conformational changes in the viologen molecular protrusions using STM and investigate changes in the width and height of the alkyl group that are due to the change in the polarity of viologen molecules by electron charges. In this experiment, high peak current is observed, such as a rectification at +1.14 V. Thus, according to the results of this experiment the rectification ratio [RR = J (at +2.5 V)/J (at -2.5 V)] of the viologen is found by 4.47 (HSC8VC8SH). Similar results are also obtained in some other cases of viologen derivatives.

Highly stable, water-dispersible metal-nanoparticle-decorated polymer nanocapsules and their catalytic applications.

A facile synthesis of highly stable, water-dispersible metal-nanoparticle-decorated polymer nanocapsules (M@CB-PNs: M=Pd, Au, and Pt) was achieved by a simple two-step process employing a polymer nanocapsule (CB-PN) made of cucurbit[6]uril (CB[6]) and metal salts. The CB-PN serves as a versatile platform where various metal nanoparticles with a controlled size can be introduced on the surface and stabilized to prepare new water-dispersible nanostructures useful for many applications. The Pd nanoparticles on CB-PN exhibit high stability and dispersibility in water as well as excellent catalytic activity and recyclability in carbon-carbon and carbon-nitrogen bond-forming reactions in aqueous medium suggesting potential applications as a green catalyst.

Strain-induced Mn valence state variation in CaMnO3-δ/substrate interfaces: electronic reconstruction versus oxygen vacancies.

This study investigates the nanoscale crystalline and electronic structures of the interfaces between CaMnO3-δ and substrates such as SrTiO3 (001) and LaAlO3 (001) by employing advanced transmission electron microscopy and electron energy loss spectroscopy techniques. The objective is to comprehend the influence of different strains on the Mn valence state. Our findings reveal that the Mn valence state remains relatively stable in the region of a weakly tensile-strained interface, whereas it experiences a significant decrease from Mn4+ to Mn2.3+ in the region of a strongly tensile-strained interface. Although this reduction in valence appears to be consistent with the electron reconstruction scenario, the observed increase in the out-of-plane lattice constant at the interface implies the accumulation of oxygen vacancies at the interface. Consequently, the present study offers a comprehensive understanding of the intricate relationships among the Mn valence state, local structure, and formation of oxygen vacancies in the context of two distinct strain cases. This knowledge is essential for tailoring the interface properties and guiding future developments in the field of oxide heterostructures.

Single carbon fiber decorated with RuO2 nanorods as a highly electrocatalytic sensing element.

We demonstrate highly efficient electocatalytic activities of single crystalline RuO(2) nanorods grown on carbon fiber (CF), i.e., RuO(2) nanorod-CF hybrid microelectrode, prepared by a simple thermal annealing process from the Ru(OH)(3) precursor at 300 °C. The general electrochemical activity of a RuO(2) nanorod-CF microelectrode represents faster electron transfer for the [Fe(CN)(6)](3-/4-) couple than that of the bare CF microelectrode which are confirmed from the cyclic voltammetry (CV) measurement. Also, the amperometric response for the H(2)O(2) oxidation is remarkably facilitated at the RuO(2) nanorod-CF microelectrode by not only the enlarged surface area but the high electrocatalytic activity of the RuO(2) nanorod material itself. Furthermore, a single microelectrode of RuO(2) nanorod-CF exhibits the superior tolerance to Cl(-) ion poisoning unlike Pt-based electrocatalysts, indicating the promising sensor candidate in physiological conditions.

Formation and superlattice of long-range-ordered self-assembled monolayers of pentafluorobenzenethiols on Au(111).

The formation and surface structure of pentafluorobenzenethiol (PFBT) self-assembled monolayers (SAMs) on Au(111) formed under various experimental conditions were examined by means of scanning tunneling microscopy (STM). Although it is well known that PFBT molecules on metal surfaces do not form ordered SAMs, we clearly revealed for the first time that the adsorption of PFBT on Au(111) at 75 degrees C for 2 h yields long-range, well-ordered self-assembled monolayers having a (2 x 5 square root(13))R30 degrees superlattice. Our results will provide new insight into controlling the structural order of PFBT SAMs, which will be very useful in precisely tailoring the interface properties of metal surfaces in electronic devices.

Vertically-Oriented WS2 Nanosheets with a Few Layers and Its Raman Enhancements.

Vertically-oriented two-dimensional (2D) tungsten disulfide (WS2) nanosheets were successfully grown on a Si substrate at a temperature range between and 550 °C via the direct chemical reaction between WCl6 and S in the gas phase. The growth process was carefully optimized by adjusting temperature, the locations of reactants and substrate, and carrier gas flow. Additionally, vertically-oriented 2D WS2 nanosheets with a few layers were tested as a surface-enhanced Raman scattering substrate for detecting rhodamine 6G (R6G) molecules where enhancement occurs from chemical enhancement by charge transfer transition from semiconductor). Raman spectra of R6G molecules adsorbed on vertically-oriented 2D WS2 nanosheets exhibited strong Raman enhancement effects up to 9.2 times greater than that on the exfoliated WS2 monolayer flake sample. From our results, we suggest that the WS2 nanosheets can be an effective surface-enhanced Raman scattering substrate for detecting target molecules.

Relation between work function and structural properties of triangular defects in 4H-SiC epitaxial layer: Kelvin probe force microscopic and spectroscopic analyses.

To understand the relationship between the work function and structural properties of sufficiently expanded triangular defects (size: ∼250 µm) in the 4H-SiC epitaxial layer, Kelvin probe force microscopy (KPFM) and spectroscopic [micro-Raman spectroscopy and photoluminescence (PL)] analyses were performed. Spectroscopic analysis demonstrated that the triangular defects mostly comprise the 3C polytypes and that it experiences internal stress, defects, and defect-induced carrier generation. The distinguishable areas in the triangular defects had surface potential values different from those of the 4H-SiC matrix; this could be explained by the work function difference, which arises from variations in the electron affinity of the 3C polytype as well as the positional variations of the Fermi energy level in terms of electron concentration. In addition, tensile-stress-induced surface disorder leading to variations in electron affinity was discussed. The mechanical properties of the triangular defects measured by a nanoindenter were significantly deteriorated because of many dislocation arrays and stacking faults with many broken and/or strained bonds.

Bi-Stability and Orientation Change of a Thin α-Fe2O3 Layer on a ε-Fe2O3 (004) Surface.

This study reports the key ingredients that influence the orientation and stability of a α-Fe2O3 layer that grows on a metastable ε-Fe2O3 during pulsed laser deposition. Depending on the substrate temperature, two different α-Fe2O3 orientations arise on the ε-Fe2O3 (004) surface. At 800 °C, (2-10)α-oriented α-Fe2O3 is stabilized, whereas at 700 °C, (006)α orientation occurs. The (2-10)α-oriented α-Fe2O3 layer possesses an interface with densely packed Fe ions with presumably considerable number of oxygen vacancies. On the other hand, the (006)α-oriented α-Fe2O3 layer is stabilized, as in the case of the YSZ (100) substrate, due to the domain pattern with an in-plane rhombic shape, which is known to become an effective nucleation site. Growth with the unexpected (2-10)α orientation can be understood based on a model that takes into account the surface energy as the dominant factor, which mainly stems from the presence of dangling bonds on the surface and the atomic vibration of the surface atoms. As the surface is one of the critical elements related to the specific functionality of a material, the present study will offer valuable insights into the designs of functional devices with novel surface properties.

Modulation of metal-insulator transitions of NdNiO3/LaNiO3/NdNiO3 trilayers via thickness control of the LaNiO3 layer.

Over the last few decades, manipulating the metal-insulator (MI) transition in perovskite oxides (ABO3) via an external control parameter has been attempted for practical purposes, but with limited success. The substitution of A-site cations is the most widely used technique to tune the MI transition. However, this method introduces unintended disorder, blurring the intrinsic properties. The present study reports the modulation of MI transitions in [10 nm-NdNiO3/t-LaNiO3/10 nm-NdNiO3/SrTiO3 (100)] trilayers (t = 5, 7, 10, and 20 nm) via the control of the LaNiO3 thickness. Upon an increase in the thickness of the LaNiO3 layer, the MI transition temperature undergoes a systematic decrease, demonstrating that bond disproportionation, the MI, and antiferromagnetic transitions are modulated by the LaNiO3 thickness. Because the bandwidth and the MI transition are determined by the Ni-O-Ni bond angle, this unexpected behavior suggests the transfer of the bond angle from the lower layer into the upper. The bond-angle transfer eventually induces a structural change of the orthorhombic structure of the middle LaNiO3 layer to match the structure of the bottom and the top NdNiO3, as evidenced by transmission electron microscopy. This engineering layer sequence opens a novel pathway to the manipulation of the key properties of oxide nickelates, such as the bond disproportionation, the MI transition, and unconventional antiferromagnetism with no impact of disorder.