b S Supporting Information ' INTRODUCTIONZnO, an IIÀVI semiconductor with noncentrosymmetric wurtzite crystal structure, a direct band gap of 3.37 eV, and a large excitation binding energy of 60 meV, has been extensively investigated because of its potential applications in piezoelectric devices, transistors, photodiodes, and photocatalysis. 1À5 The unique antibacterial function of ZnO nanostructures both in the dark and under solar irradiation has also attracted great interest. 6,7 In the field of photocatalysis, ZnO is usually believed to be an alternative photocatalyst material to TiO 2 , since they have similar band gaps and similar photocatalytic mechanisms. 4,5 In addition, it was reported in several works that ZnO exhibited better activity than TiO 2 for the photocatalytic degradation of environmental pollutants, especially for the decomposition of dyes under visible irradiation. 8À10 The structure of nanomaterial, including morphology, particle size, and two-dimensional and three-dimensional architectures, can play important roles in determining the electrical, optical, and catalytic properties. A large volume of work have been done to elucidate the structureÀproperty relationship in heterogeneous catalysis and to provide useful information for the design and building of efficient nanostructured catalysts. The morphology, particle size, crystal orientation, crystallinity, and oxygen defects are some factors that influence the photocatalytic performance and stability of ZnO photocatalysts. ZnO nanostructure with different three-dimensional architectures, such as microscale rods, tubes, plates, porous hollow microspheres, and flowerlike hierarchical micro/nanoarchitecture, were fabricated by chemical vapor deposition, thermal evaporation, and
Formation of π−π stacked lamellar structure is important for high performance organic semiconductor materials. We previously demonstrated that perfluoroalkylation of aromatics and heteroaromatics was one of the strategies to design organic crystalline materials with π−π stacked lamellar structures while improving air stability as a result of the strong electron withdrawing ability of perfluoroalkyl substituents. Square-planar transition metal complexes with large π-conjugated ligands are also an important category of semiconductor materials. We have perfluoroalkylated square-planar transition metal complexes, leading to the formation of a π−π stacked lamellar crystal packing motif in the solid state. Here we report six crystal structures of Pd and Pt complexes with bis-perfluorobutylated catechol ligand as one of the two ligands that bonds to the metal centers. This structural design possesses similar molecular topology when compared to perfluoroalkylated aromatics and heteroaromatics we have reported previously, again, demonstrating the steering power of the perfluoroalkyl substituents in engineering organic and organometallic solid state materials.
Analysis of amino acids is crucial to protein structure elucidation. Amino acids, amenable to separation by liquid chromatography (LC), can be detected by sensitive detectors used in liquid chromatograph including absorbance, fluorescence or electrochemical detector when derivatized. Derivatization of amino acids using suitable reagents enhances the separation and detection of amino acids using liquid chromatography. Sanger's reagent (1-fluoro-2,4-dinitrobenzene, DNFB) makes amino acids suitable for absorbance detection. However, little has been done in terms of liquid chromatography with electrochemical detection (LC-EC) of the DNFB derivatized amino acids. Furthermore, sensor development based on electrochemistry of nitroaromatics has increased dramatically for explosive detection. Since nitroaromatics are electrochemically active, it is essential to determine the reduction pathway. Cyclic voltammetry (CV), rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) experiments have been performed on nitrobenzene (NB) and N-methyl-2,4-dinitroaniline (NMDNA). The results showed that the nitro group was reduced to hydroxylamine in aqueous solutions by addition of four electrons and four protons per nitro group and the hydroxylamine can be reversibly oxidized into a nitroso by removal of two electrons and two protons. Electrochemical detection of the nitro groups is appropriate for dual electrode detection of DNFB labeled amino acids in which reduction can occur on an upstream electrode and corresponding oxidation of the reduction product occurs on the downstream electrode.
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