Bonding structure analysis of carbon nitride films by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS)

Carbon nitride films were prepared by an opposed-target DC reactive sputtering system and the bonding behaviors were investigated according to the nitrogen content and annealing temperature. Annealing leads to a loss of nitrogen from the films and the CN is totally removed at 600 °C. Due to annealing at 600 °C, the C---C out-of-plane vibrational band intensity at 700 cm⁻¹ becomes very low and also the CN band at 2200 cm⁻¹ disappears completely. The sp² bonding in a CN compound is the most stable phase. Due to carbon's atypical nature in having its p orbital more compact and tightly bound compared to s states, the C=N sp² phase is more stable than the C---C sp³ phase. As the C=N sp² phase dominates the structure, the film is mainly graphite-like with some proportion of C---C, CN and N=N bonds.     

Chemically dealloyed Pt–Au–Cu ternary electrocatalysts with enhanced stability in electrochemical oxygen reduction

We report simple synthesis of ternary Pt–Au–Cu catalysts consisting of active Pt-rich shell and Pt transition-metal alloy core for use as highly active and durable electrocatalysts in oxygen reduction reactions. The ternary Pt–Au–Cu catalysts were synthesized by chemical coreduction followed by thermal treatment and chemical dealloying. During synthesis, thermal treatment formed metal particles into high-degree alloys, and chemical dealloying led to selective dissolution of soluble Cu species from the outer surface layer of the thermally treated alloy particles, resulting in Pt-based alloys@Pt-rich surface core–shell configuration. Compared with a commercial Pt/C catalyst, our Pt_1?xAu _x Cu₃/C-AT catalysts exhibited approximately 2.4-fold enhanced performance in oxygen reduction reactions. Among the catalysts employed in this work, Pt_0.97Au_0.3Cu₃/C-AT showed the highest performance in terms of mass activity, specific activity, and electrochemically active surface area loss with negligible change during 10,000 potential cycles. The synthesis details, electrochemical characteristics, oxygen reduction reaction performance, and durability of the chemically dealloyed ternary Pt–Au–Cu catalysts are presented and discussed.     

Spontaneous surface flattening via layer-by-layer assembly of interdiffusing polyelectrolyte multilayers

We report a facile means to achieve planarization of nonflat or patterned surfaces by utilizing the layer-by-layer (LbL) assembly of highly diffusive polyelectrolytes. The polyelectrolyte pair of linear polyethylenimine (LPEI) and poly(acrylic acid) (PAA) is known to maintain intrinsic diffusive mobility atop or even inside ionically complexed films prepared by LbL deposition. Under highly hydrated and swollen conditions during the sequential film buildup process, the LbL-assembled film of LPEI/PAA undergoes a topological self-deformation for minimizing surface area to satisfy the minimum-energy state of the surface, which eventually induces surface planarization along with spontaneous filling of surface textures or nonflat structures. This result is clearly different from other cases of applying nondiffusive polyelectrolytes onto patterned surfaces or confined structures, wherein surface roughening or incomplete filling is developed with the LbL assembly. Therefore, the approach proposed in this study can readily allow for surface planarization with the deposition of a relatively thin layer of polyelectrolyte multilayers. In addition, this strategy of planarization was extended to the surface modification of an indium tin oxide (ITO) substrate, where surface smoothing and enhanced optical transmittance were obtained without sacrificing the electronic conductivity. Furthermore, we investigated the potential applicability of surface-treated ITO substrates as photoelectrodes of dye-sensitized solar cells prepared at room temperature. As a result, an enhanced photoconversion efficiency and improved device characteristics were obtained because of the synergistic role of polyelectrolyte deposition in improving the optical properties and acting as a blocking layer to prevent electron recombination with the electrolytes.     

Chromofluorescent indicator for intracellular Zn2+/Hg2+ dynamic exchange

The fluorescence of NABQ increases remarkably in the presence of Zn(2+) and is quenched by Hg(2+). As shown by confocal imaging, NABQ-Zn(2+) can penetrate cells, where the bound Zn(2+) is exchanged for Hg(2+). This results in the concomitant export of Hg(2+) from the cells, showing that NABQ can act as a Zn(2+) carrier and as a Hg(2+) extracting agent in living cells.     

Effects of ion-pairing and hydration on the SNAr reaction of the F- with p-chlorobenzonitrile in aprotic solvents

Theoretical ab initio calculations including liquid phase optimizations were used to investigate the S(N)Ar reaction of the fluoride ion with p-chlorobenzonitrile in dimethyl sulfoxide solution. The effect of the counter ion and hydration of the fluoride ion with one water molecule was analyzed. The calculations indicate that the gas-phase S(N)Ar reaction is more favorable than the corresponding S(N)2 reactions involving fluoride ion and 2-chlorobutane. However, the substantially higher solvent effect on the S(N)Ar reaction makes the nucleophilic substitution on the aromatic ring less favorable than the aliphatic reaction in the liquid phase. For the anhydrous tetrabutylammonium fluoride system, the theoretical free energy barrier of 22.1 kcal mol(-1) is close to the experimental one of 24.4 kcal mol(-1). The smaller tetramethylammonium cation strongly associates with the fluoride ion and increases the barrier by 5 kcal mol(-1). Similarly, just one water molecule hydrating the fluoride ion has the same effect. An analysis of the reaction involving the ion pair and the free anion in different polarity media predicts an unexpected behavior and indicates there is an ideal solvent polarity for each counter ion.     

Complex pattern formation by adhesion-controlled anisotropic wrinkling

We report complex pattern formation and shape control in the confinement-induced wrinkling that occurs when a poly(dimethylsiloxane) (PDMS) mold is placed on a bilayer of metal and polymer and then heated. Various complex structures that are different from the mold pattern form through the self-organization of wrinkles. These complex structures could be inverted in shape by manipulating the work of adhesion at the interface between the mold and the metal surface. Convex wrinkles result when the work of adhesion is relatively large. However, inverted concave wrinkles emerge when it is relatively small. The ratio of the mold period to the intrinsic wrinkling wavelength is another factor that determines the shape. The ability to tailor the shape of a surface is expected to have a broad range of applications in electro-optics and microfluidics.     

Optical spectra of aqueous solutions of glutamine-tryptophan associates

The optical density and luminescence ability of aqueous solutions of glutamine-tryptophan depend on the degree of oxidation of the initial dry substances of dipeptide. Glutamine-tryptophan has a high associating ability, which increases if stored. The general form of the optical absorption and luminescence spectra of the associates differs little from the spectra of monomers. Among the spectral-optical symptoms of association of a substance in a solution for glutamine-tryptophan, we discovered the hypochromism and narrowing of the absorption spectra and shortening of the fluorescence lifetime. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 436–439, July–August, 2000.