Water-phase synthesis of Au and Au-Ag nanowires and their SERS activity.

Metal nanowires (NWs) with a diameter of a few nanometers have attracted considerable attention as a promising one-dimensional nanomaterial due to their inherent flexibility and conductive properties and their weak plasmon absorption in the visible region. In a previous paper, we reported the synthesis of ultrathin 1.8 nm-diameter Au NWs using toluene-solubilized aqueous solutions of a long-chain amidoamine derivative (C18AA). This study investigates the effect of different organic solvents solubilized in C18AA aqueous solutions on the morphology of the Au products and demonstrates that solubilizing methylcyclohexane yields thick 2.7 nm-diameter Au NWs and 3.3 nm-diameter Au-Ag alloy NWs. Further, the surface-enhanced Raman scattering sensitivity of ultrathin Au NWs, thick Au NWs, and thick Au-Ag alloy NWs were assessed using 4-mercaptopyridine and found that their enhancement factors are 104-105 and the order is Au-Ag NWs > thick Au NWs > ultrathin Au NWs.

Hole, Convex, and Silver Nanoparticle Patterning on Polystyrene Nanosheets by Colloidal Photolithography at Air-Water Interfaces.

Colloidal photolithography is a versatile advanced technique for fabricating periodic nanopatterned arrays, with patterns carved exclusively on photoresist films deposited on solid substrates in a typical photolithographic process. In this study, we apply colloidal photolithography to polystyrene (PS) films half-covered with poly(methyl methacrylate) (PMMA) colloids at the air-water interface and demonstrate that periodic hole structures can be carved in PS films by two processes: photodecomposing PS films with ultraviolet (UV) light and removing PMMA colloids with a fluorinated solvent. Nonspherical holes, such as C-shaped and chiral comma-shaped holes, are also fabricated by regulating the UV illumination conditions. Furthermore, in addition to holes, convex patterns on PS films are realized by combining weak UV illumination with solvent treatment. We also demonstrate that actively using the water surface as the UV illumination field enables periodic silver nanoparticle spots to be deposited on PS films simply by dissolving silver ions in the water phase.

Detection of Fe3+ and Hg2+ ions through photoluminescence quenching of carbon dots derived from urea and bitter tea oil residue.

In this study, we prepared nitrogen-doped carbon dots (xNCDs) using hydrothermally-treated bitter tea oil residue with urea for the detection of metal ions by monitoring the photoluminescence quenching. The quantum yields of the xNCDs increased from approximately 3.85% (CDs) to 5.5% (3NCDs) and 7.2% (1NCDs), revealing that nitrogen doping effectively increases the fluorescence emission. The increased emission of the xNCDs can be attributed to radiative recombination resulting from the π-π* transition of the C=C or the n-π* transition between the C=O or N=O of sp3 units. Moreover, the CDs have abundant surface-attached phenolic and hydroxyl groups that coordinate with Fe3+ ions and quench the fluorescence. Conversely, Hg2+ ions preferentially adsorb on nitrogen-containing groups, such as amide-carbonyl groups (O=C-NH2) and pyridinic and pyrrolic functionalities, on the surface of the NCDs owing to their strong affinity, quenching the substantial photoluminescence emissions. Our results suggest that bitter tea oil residue-derived carbon dots can be used to selectively detect metal ions, such as Fe3+ and Hg2+, by doping with nitrogen using urea as a nitrogen precursor.

Thermally Tunable Structural Coloration of Water/Surfactant/Oil Emulsions.

Stimuli-responsive structural color in nature has fascinated scientists, directing them to develop artificial coloration materials that adjust colors in response to external stimuli. Many stimuli-responsive structural color materials have been realized. However, only a few have reported on all-liquid-type materials, which have a particularly desirable feature because they impart their function to the device of any shape. We have previously reported the development of a consistent structural color within a narrow temperature range for all-liquid-type emulsions comprising a long-chain amidoamine derivative (C18AA) and tetraoctylammonium bromide (TOAB). In the present study, we demonstrate that introducing NaCl as an electrolyte affords a highly thermo-sensitive color-changing ability to the emulsions. The structural color of the emulsions can be controlled from red to blue by tuning the temperature. Furthermore, the C18AA and TOAB concentrations can independently regulate the color and coloring-temperature, respectively, realizing that the desired color can develop at a given temperature.

Photoluminescence quenching of thermally treated waste-derived carbon dots for selective metal ion sensing.

In the present study, carbon-dots (CDs) were derived from the thermal oxidation of an agricultural waste, bitter tea residue, to obtain different sp2/sp3 ratios and electronic structures for metal sensing. The CDs obtained from calcination at 700 °C exhibited the highest photoluminescence (PL) quantum yield (QY) of 11.8% among all the samples treated at different temperatures. These CDs had a high degree of graphitization, which resulted in a strong π-π* electron transition, and hence in a high QY. The strong photoluminescence of the CDs could be used to sense the metal ions Ag+, Sr2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, and Sn2+ by monitoring their PL intensity at an excitation wavelength of 320 nm. The metals inhibited the PL intensity in the order Ag+ > Fe2+, Fe3+, Ni2+ > Sr2+, Co2+, Cu2+, Sn2+, which demonstrated that the CDs exhibited high metal ion detection capability and selectivity. The detection of Fe3+ using CDs was performed in the range of 10-100 ppm with a LOD (limit of detection) value of 0.380 ppm. Theoretical calculations demonstrated that Ag+, Sr2+, and Sn2+ induced charge transfer excitation and that Fe2+ and Ni2+ induced d-d transitions via complexation with the sp2 clusters. The charge transfer excitation and d-d transitions hindered the π-π* transition of the sp2 clusters, leading to a quenching effect. On the other hand, Li+, Na+, and K+ ions did not alter the π-π* transition of the sp2 clusters, resulting in a negligible quenching effect. In summary, the oxidation level and electronic structure of CDs derived from bitter tea residue could be tailored, and the CDs were shown to be a facile, sustainable, and eco-friendly material for metal sensing.

Conductive nanosheets produced by UV irradiation of a Ag nanoparticle monolayer at the air-water interface.

In a previous study, we demonstrated that conductive Au nanosheets can be prepared by UV irradiation of an Au nanoparticle monolayer spreading on water. In this study, we applied this UV irradiation technique to inexpensive Ag nanoparticles (NPs) to expand their versatility. UV irradiation of Ag NPs on water resulted in the formation of large Ag NPs and was ineffective for preparing conductive Ag films. The solubilization of additives in the water phase, however, resulted in the conversion of the large Ag NPs into a nanosheet, and the solubilization method was highly effective for preparing transparent conductive Ag films with an optical transmittance of above 70%.

Iron Oxyhydroxide Hierarchical Micro/Nanostructured Film as Catalyst for Electrochemical Oxygen Evolution Reaction.

A key requirement in developing oxygen evolution reaction (OER) electrocatalysts is increasing their surface area. Herein, we report the design of a hierarchical micro/nanostructured catalyst. Based on polystyrene colloidal template electrodeposition, an ordered microcup array surrounded by nanoflakes was fabricated. The effect of the deposition time on the formation of the catalyst and the corresponding OER performance of the catalyst were investigated using scanning electron microscopy, in situ X-ray absorption fine structure (XAFS) spectroscopy, and electrochemical analysis. The in situ XAFS measurements indicate that the structure of the hierarchical structured catalyst is similar to that of γ-FeOOH. The electrochemical analysis indicates that the hierarchical catalyst has a large surface area and a low charge transfer resistance, which lead to its excellent catalytic performance for the OER. Our study provides new insights in designing high-performance OER catalysts. Moreover, the synthesized hierarchical micro/nanostructured catalyst could be used as a platform for further studies on low-cost iron-based electrocatalysts.

Photocatalytic Dye and Cr(VI) Degradation Using a Metal-Free Polymeric g-C3N4 Synthesized from Solvent-Treated Urea.

The development of visible-light-driven polymeric g-C3N4 is in response to an emerging demand for the photocatalytic dye degradation and reduction of hexavalent chromium ions. We report the synthesis of g-C3N4 from urea treated with various solvents such as methanol, ethanol, and ethylene glycol. The samples were characterized and the Williamson⁻Hall method was applied to investigate the lattice strain of the samples. The activity of the samples was evaluated by observing the degradation of methyl orange and K2Cr2O7 solution under light irradiation. Photocatalytic reaction kinetics were determined as pseudo-first-order and zero-order for the degradation of methyl orange and reduction of hexavalent chromium, respectively. Due to the inhibited charge separation resulting from the small lattice strain, reduced crystal imperfection, and sheet-like structure, g-C3N4 obtained from ethanol-treated urea exhibited the highest activity among the evaluated samples.

Extensibility effect of poly(3-hexylthiophene) on the glucose sensing performance of mixed poly(3-hexylthiophene)/octadecylamine/glucose oxidase Langmuir-Blodgett films.

Poly(3-hexylthiophene) (P3HT) is utilized as a material to enhance the glucose sensing performance of glucose oxidase (GOx) Langmuir-Blodgett (LB) films. To enhance the extensibility and homogeneity of the P3HT in the LB films, octadecylamine (ODA) is introduced. The characteristics of the mixed P3HT/ODA Langmuir monolayers are investigated first and then, utilized as template layers to adsorb GOx from the subphase, preparing P3HT/ODA/GOx Langmuir-Blodgett films for glucose sensing. The results show that P3HT molecules tend to aggregate at the air/liquid interface and, furthermore, the P3HT monolayer has a weak ability to adsorb GOx from the subphase. By using mixed P3HT/ODA monolayer, the presence of ODA not only inhibits the aggregation of P3HT, but also increases the adsorption ability of the monolayer to GOx. The extensibility of P3HT and the homogeneity of the P3HT/ODA monolayers are closely related to the concentration of P3HT/ODA stock solutions. On the glucose sensing experiments, the performance of the P3HT/ODA/GOx LB film is greatly improved due to the presence of P3HT and, furthermore, the sensibility increases with increasing extensibility of P3HT molecules. The best sensitivity achieved for the P3HT/ODA/GOx film is 5.4µAmM-1cm-2 which is over two times the value obtained by the ODA/GOx film (2.3µAmM-1cm-2).

Atom Transfer Radical Addition/Polymerization of Perfluorosulfonic Acid Polymer with the C-F Bonds as Reactive Sites.

This work reports the first demonstration of the chemical reactions on the C-F groups of perfluorosulfonic acid polymers. The Nafion chains show chemical reactivity for atom transfer radical addition onto multiwalled carbon nanotubes and ability to serve as a macroinitiator for atom transfer radical polymerization. The C-F groups and mainchain -CF2 groups have been demonstrated, under a study with 19F NMR, as the active sites responsible for the reactions. The results could certainly extend both the scopes of chemistry and application of perfluorosulfonic acid polymers as well as the windows of atom transfer radical addition/polymerization to fluorinated compounds.

Headgroup effects of template monolayers on the adsorption behavior and conformation of glucose oxidase adsorbed at air/liquid interfaces.

Stearic acid (SA) and octadecylamine (ODA) monolayers at the air/liquid interface were used as template layers to adsorb glucose oxidase (GOx) from aqueous solution. The effect of the template monolayers on the adsorption behavior of GOx was studied in terms of the variation of surface pressure, the evolution of surface morphology observed by BAM and AFM, and the conformation of adsorbed GOx. The results show that the presence of a template monolayer can enhance the adsorption rate of GOx; furthermore, ODA has a higher ability, compared to SA, to adsorb GOx, which is attributed to the electrostatic attractive interaction between ODA and GOx. For adsorption performed on a bare surface or on an SA monolayer, the surface pressure approaches an equilibrium value (ca. 8 mN/m) after 2 to 3 h of adsorption and remains nearly constant in the following adsorption process. For the adsorption on an ODA monolayer, the surface pressure will increase further 1 to 2 h after approaching the first equilibrium pressure, which is termed the second adsorption stage. The measurement of circular dichroism (CD) spectroscopy indicates that the Langmuir-Blodgett films of adsorbed GOx transferred at the first equilibrium state (π = 8 mN/m) have mainly a ß-sheet conformation, which is independent of the type of template monolayers. However, the ODA/GOx LB film transferred at the second adsorption stage has mainly an α-helix conformation. It is concluded that the specific interaction between ODA and GOx not only leads to a higher adsorption rate and adsorbed amount of GOx but also induces a conformation change in adsorbed GOx from ß-sheet to α-helix. The present results indicate that is possible to control the conformation of adsorbed protein by selecting the appropriate template monolayer.