Surface-confined Reaction Research Articles

Halogen-Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins.

The product distribution in direct alkane functionalization by oxyhalogenation strongly depends on the halogen of choice. We demonstrate that the superior selectivity to olefins over an iron phosphate catalyst in oxychlorination is the consequence of a surface-confined reaction. By contrast, in oxybromination alkane activation follows a gas-phase radical-chain mechanism and yields a mixture of alkyl bromide, cracking, and combustion products. Surface-coverage analysis of the catalyst and identification of gas-phase radicals in operando mode are correlated to the catalytic performance by a multi-technique approach, which combines kinetic studies with advanced characterization techniques such as prompt-gamma activation analysis and photoelectron photoion coincidence spectroscopy. Rationalization of gas-phase and surface contributions by density functional theory reveals that the molecular level effects of chlorine are pivotal in determining the stark selectivity differences. These results provide strategies for unraveling detailed mechanisms within complex reaction networks.

NOBF4-Functionalized Au-Fe3O4 Nanoheterodimers for Radiation Therapy: Synergy Effect Due to Simultaneous Reactive Oxygen and Nitrogen Species Formation.

Snowman-shaped Au-Fe3O4 nanoheterodimers were synthesized by thermal decomposition of iron oleate on presynthesized Au nanoparticles. Subsequently performed ligand exchange with nitrosyl tetrafluoroborate provided water solubility and enabled X-ray-induced NO release. These Au-Fe3O4 nanoheterodimers combine high- Z material with catalytically active Fe3O4 surfaces and, moreover, plasmonic properties with superparamagnetic performance. We could establish synergetic interactions between X-radiation and both the Au and Fe3O4 surfaces, which resulted in the simultaneous production of the nitric oxide radical at the Fe3O4 surface and the superoxide radical at the Au surface. The surface-confined reaction between these radicals generated peroxynitrite. This highly reactive species may cause nitration of mitochondrial proteins and lipid peroxidation and induce DNA strand breaks. Therefore, high concentrations of peroxynitrite are expected to give rise to severe cellular energetic derangements and thereupon entail rapid cell death. As providing a common platform for X-ray-induced formation of the highly reactive radical nitric oxide, superoxide, and peroxynitrite, nitrosyl tetrafluoroborate functionalized Au-Fe3O4 nanosnowmen were shown to exhibit excellent performance as X-ray-enhancing agents in radiation therapy.

Reaction between Pyridine and CH3NH3PbI3: Surface-Confined Reaction or Bulk Transformation?

Pyridine molecules have been used to passivate surface Pb2+ sites of CH3NH3PbI3, to recrystallize CH3NH3PbI3, and to bleach CH3NH3PbI3. However, these results contradict each other, as recrystallization and optical-bleach require transformation of bulk CH3NH3PbI3, but surface passivation demands the confinement of the reaction at the surface region. The underlying mechanism for these seemly contradicting results is not yet understood. In this paper, we show, at 25 °C, partial pressure of pyridine vapor is a determining factor for its reaction behaviors with CH3NH3PbI3: one can modify the surface region of CH3NH3PbI3 by using pyridine vapor of pressure 1.15 torr or lower but can transform the whole bulk CH3NH3PbI3 film with a pyridine vapor of 1.3 torr or higher. Our result is the first demonstration that the reaction modes, i.e., surface-confined reaction and bulk transformation, are very sensitive to the partial pressure of under-saturated pyridine vapor. Despite the different reaction behaviors, it is interesting that in all pressure ranges, pyridinium ion is a main product from the reaction between pyridine and CH3NH3PbI3. The bulk transformation is due to the formation of a liquid-like film, which increases the mobility of species to catalyze the reaction between pyridine and CH3NH3PbI3. It is important to note 1.3 torr is much smaller than the saturated vapor pressure of pyridine (20 torr at 25 °C). These findings provide a guidance in applying pyridine and other amines to functionalize and transform CH3NH3PbI3 and other hybrid halide perovskites. It also highlights the critical role of fundamental studies in controllably modifying CH3NH3PbI3.

Biosensor based on glucose oxidase-nanoporous gold co-catalysis for glucose detection

Promoting the electrocatalytic oxidation of glucose is crucial in glucose biosensor design. In this study, nanoporous gold (NPG) was selected for glucose oxidase (GOx) immobilization and glucose biosensor fabrication because of its open, highly conductive, biocompatible, and interconnected porous structure, which also facilitates the electrocatalytic oxidation of glucose. The electrochemical reaction on the surface of the resulting GOx/NPG/GCE bioelectrode was attributed to the co-catalysis effect of GOx and NPG. A surface-confined reaction in a phosphate buffer solution was observed at the bioelectrode during cyclic voltammetry experiments. Linear responses were observed for large glucose concentrations ranging from 50μM to 10mM, with a high sensitivity of 12.1μAmM−1cm−2 and a low detection limit of 1.02μM. Furthermore, the GOx/NPG/GCE bioelectrode presented strong anti-interference capability against cholesterol, urea, tributyrin, ascorbic acid, and uric acid, along with a long shelf-life. For the detection of glucose in human serum, the data generated by the GOx/NPG/GCE bioelectrode were in good agreement with those produced by an automatic biochemical analyzer. These unique properties make the GOx/NPG/GCE bioelectrode an excellent choice for the construction of a glucose biosensor.

Lipase-nanoporous gold biocomposite modified electrode for reliable detection of triglycerides

For triglycerides biosensor design, protein immobilization is necessary to create the interface between the enzyme and the electrode. In this study, a glassy carbon electrode (GCE) was modified with lipase-nanoporous gold (NPG) biocomposite (denoted as lipase/NPG/GCE). Due to highly conductive, porous, and biocompatible three-dimensional structure, NPG is suitable for enzyme immobilization. In cyclic voltammetry experiments, the lipase/NPG/GCE bioelectrode displayed surface-confined reaction in a phosphate buffer solution. Linear responses were obtained for tributyrin concentrations ranging from 50 to 250mgdl−1 and olive oil concentrations ranging from 10 to 200mgdl−1. The value of apparent Michaelis–Menten constant for tributyrin was 10.67mgdl−1 and the detection limit was 2.68mgdl−1. Further, the lipase/NPG/GCE bioelectrode had strong anti-interference ability against urea, glucose, cholesterol, and uric acid as well as a long shelf-life. For the detection of triglycerides in human serum, the values given by the lipase/NPG/GCE bioelectrode were in good agreement with those of an automatic biochemical analyzer. These properties along with a long self-life make the lipase/NPG/GCE bioelectrode an excellent choice for the construction of triglycerides biosensor.

Surface-Confined Reaction of Aliphatic Diamines with Aromatic Diisocyanates on Au{111} Leads to Ordered Oligomer Assemblies

The surface-confined reaction of 1,4-diaminobutane with 1,3- and 1,4-phenylene diisocyanate on Au{111} was investigated by scanning tunnelling microscopy in ultrahigh vacuum. For both the m- and p-phenylene diisocyanates, the nucleophilic addition reaction to form oligourea species occurred at, or slightly above, 300 K. Subsequent annealing allows oligomers to form extended ordered assemblies that density functional theory reveals are stabilized by intermolecular H-bonding interactions.

Functionalized graphene oxide for clinical glucose biosensing in urine and serum samples

A novel clinical glucose biosensor fabricated using functionalized metalloid-polymer (silver-silica coated with polyethylene glycol) hybrid nanoparticles on the surface of a graphene oxide nanosheet is reported. The cyclic voltammetric response of glucose oxidase modification on the surface of a functionalized graphene oxide electrode showed a surface-confined reaction and an effective redox potential near zero volts, with a wide linearity of 0.1–20 mM and a sensitivity of 7.66 μA mM−1 cm−2. The functionalized graphene oxide electrode showed a better electrocatalytic response toward oxidation of H2O2 and reduction of oxygen. The practical applicability of the functionalized graphene oxide electrode was demonstrated by measuring the peak current against multiple urine and serum samples from diabetic patients. This new hybrid nanoarchitecture combining a three-dimensional metalloid-polymer hybrid and two-dimensional graphene oxide provided a thin solid laminate on the electrode surface. The easy fabrication process and retention of bioactive immobilized enzymes on the functionalized graphene oxide electrode could potentially be extended to detection of other biomolecules, and have broad applications in electrochemical biosensing.

Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked--i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOT oligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations.

Quantitative Kinetic Measurements of the Esterification of Self-Assembled Monolayers of Mercaptoundecanol by Trifluoroacetic Anhydride Using Friction Force Microscopy

Central to the advancement of friction force microscopy (FFM) as a quantitative surface analysis technique is the establishment of clear relationships between the organization and composition of surfaces and data acquired from FFM. As a step toward this goal, FFM has been applied to measurement of the kinetics of a surface-confined reaction, namely, the esterification of alcohol-terminated self-assembled monolayers (SAMs) by trifluoroacetic anhydride. The kinetics were studied initially using contact angle goniometry. The data obtained were found to be well described by a Langmuir adsorption isotherm. The progress of the reaction was also monitored by X-ray photoelectron spectroscopy, and comparative studies carried out using FFM. By using a simple numerical analysis of the FFM data, it has been possible to obtain quantitative information on surface composition. The resulting measurements of the fraction of derivatized molecules have been compared with compositional data obtained from XPS and contact angle goniometry, and found to be in excellent agreement, establishing unequivocally the capability of FFM as a quantitative surface analysis technique.

Oxidation of Si during the growth ofSiOxby ion-beam sputter deposition:In situx-ray photoelectron spectroscopy as a function of oxygen partial pressure and deposition temperature

Oxidation of silicon during the growth of silicon oxide by ion beam sputter deposition was studied by in situ x-ray photoelectron spectroscopy as a function of oxygen partial pressure at various deposition temperatures below $600\phantom{\rule{0.2em}{0ex}}\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$. At low temperatures, the variation of incorporated oxygen content is similar to a dissociative adsorption isotherm of ${\mathrm{O}}_{2}$ on Si indicating that the surface-confined reaction of the deposited Si atoms with the adsorbed oxygen atoms is the main process. However, it shows a three-step variation with the oxygen partial pressure at high temperatures. The evolution of $\mathrm{SiO}$ species confirmed by the XPS indicates that an adsorption-induced surface reaction and a diffusion-induced internal reaction are the main pathways for the Si oxidation.

Time-resolved Near Infrared Surface-enhanced Raman Scattering Spectroscopy of a Surface-confined Electrochemical Reaction

Abstract A time-resolved surface-enhanced Raman scattering (SERS) system was developed using a step-scan near-infrared Fourier transform(FT) spectrometer. The developed system with a submillisecond time resolution was applied to a surface-confined reaction of totally two-electron redox of 9,10-phenanthrenequinone(PQ). From the electrochemical and spectroscopic results, the standard electrochemical rate constant was calculated to be 0.08 s−1 for PQ adsorbed on a Au electrode.