Silica Nanochannel Array Film Supported by ß-Cyclodextrin-Functionalized Graphene Modified Gold Film Electrode for Sensitive and Direct Electroanalysis of Acetaminophen

Convenient and sensitive detection of active analytes in complex matrix is crucial in biological, medical, and environmental analysis. Silica nanochannel array film (SNF) equipped electrochemical sensors have shown excellent anti-fouling performance in direct analysis of complex samples. In this work, we demonstrated an electrochemical sensor with anti-fouling performance for highly sensitive detection of acetaminophen (APAP) based on SNF supported by ß-cyclodextrin-graphene (CDG) nanocomposite modified Au film electrode (AuF). Because of their rich surface hydroxyls and 2D lamellar structure, CDG on AuF can serve as the nanoadhesive for compact binding SNF, which can be grown by electrochemical assisted self-assembly method in a few seconds. Attributable to the electrocatalytic property of graphene and the synergistic enrichment from both CD and SNF nanochannels towards analyte, the SNF/CDG/AuF sensor demonstrates sensitive detection of acetaminophen ranged from 0.2 to 50 μM with an ultralow limit-of-detection of 14 nM. Taking advantage of the anti-fouling ability of SNF, the sensor is able to realize accurate and convenient analysis of APAP in commercially available paracetamol tablets.

Quantitative structure determination of adsorbed formate and surface hydroxyls on Fe3O4(001)

Quantitative determination of the adsorption site of hydroxyl and formate species formed during the adsorption of formic acid on Fe3O4(001).

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for the chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not clarified yet. We address this question by Density Functional Theory (DFT) and <i>ab initio</i> molecular dynamics (AIMD) in combination with the Bluemoon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = <i>N</i>,<i>N</i>,<i>N’</i>,<i>N’</i>-tetramethylethylenediamine) show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyls plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.<br>

Investigating the Effects of Surface Adsorbates on Gold and Palladium Deposition on Carbon

Surface functional groups have a strong influence on the deposition and final state of nanoparticles adsorbed on to the surface, a role discussed by Professor Spencer in his work. This tribute to Spencer explores the formation of hydroxyls, thiosulfates, sulfites and sulfur atoms on carbon (HOPG) surfaces and their effect on the deposition of gold and palladium from aqueous solutions. Hydroxyls formed from ammonium hydroxide treatment have identical behaviour to those formed by acid treatment, and gold adsorption from Au3+ solutions gives Au0 initially, with Au3+ formed at higher concentrations on these surfaces. In contrast, palladium adsorption is hindered by the presence of the hydroxyls and there is no indication of any reduction to the metallic state. Ammonium thiosulfate adsorbs dissociatively from aqueous solutions on HOPG if the surface is pre-activated by the presence of surface hydroxyls. At low concentrations of ammonium thiosulfate, adsorbed sulfite and sulfur are formed in equimolar concentrations whereas adsorption of high concentrations of ammonium thiosulfate gives some degree of molecular adsorption, with evidence in XP spectra for an ammonium ion and a sulfur 2p peak at 282.9 eV attributed to the undissociated thiosulfate ion. Both sulfur and the sulfite are stable at the surface in neutral solutions but the sulfite desorbs when treated with acidified solutions (~ pH ≤ 6). These two groups are also stable at 373 K but begin to desorb by 473 K. Exposure to a weak chloroauric acid solution causes the desorption of the sulfite and formation of a gold species with an XP binding energy of 84.6 eV; we cannot determine from the present data whether this peak is due to a Au(I) state or very small nanoparticles of Au(0). Graphic Abstract

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

<p>Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for the chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond cleavage mechanism on the growth surface is not clarified yet. We address this question by Density Functional Theory (DFT) and <i>ab initio</i> molecular dynamics (AIMD) in combination with the Bluemoon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = <i>N</i>,<i>N</i>,<i>N’</i>,<i>N’</i>-tetramethylethylenediamine) show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyls plays a key role in aiding the cleavage of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.<b></b></p>

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

<p>Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for the chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond cleavage mechanism on the growth surface is not clarified yet. We address this question by Density Functional Theory (DFT) and <i>ab initio</i> molecular dynamics (AIMD) in combination with the Bluemoon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = <i>N</i>,<i>N</i>,<i>N’</i>,<i>N’</i>-tetramethylethylenediamine) show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyls plays a key role in aiding the cleavage of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.<b></b></p>