Oxidation of tertiary amine-derivatized surfaces to control protein adhesion

Selective oxidation of omega-tertiary amine self-assembled thiol monolayers to tertiary amine N-oxides is shown to transform the adhesion of model proteins lysozyme and fibrinogen upon them. Efficient preparation of both secondary and tertiary linker amides as judged by X-ray photoelectron spectroscopy (XPS) and water droplet contact angle was achieved with an improved amide bond formation on gold quartz crystal microbalance (QCM) sensors using 2-(1H-7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyl hexafluorophosphate methanaminium uronium (HATU). Oxidation with hydrogen peroxide was similarly assessed, and adhesion of lysozyme and fibrinogen from phosphate buffered saline was then assayed by QCM and imaged by AFM. Tertiary amine-functionalized sensors adsorbed multilayers of aggregated lysozyme, whereas tertiary amine N-oxides and triethylene glycol-terminated monolayers are consistent with small protein aggregates. The surface containing a dimethylamine N-oxide headgroup and ethyl secondary amide linker showed the largest difference in adsorption of both proteins. Oxidation of tertiary amine decorated surfaces therefore holds the potential for selective deposition of proteins and cells through masking and other patterning techniques

Literature survey on oxidations and fatigue lives at elevated temperatures

Nickel-base superalloys are the most complex and the most widely used for high temperature applications such as aircraft engine components. The desirable properties of nickel-base superalloys at high temperatures are tensile strength, thermomechanical fatigue resistance, low thermal expansion, as well as oxidation resistance. At elevated temperature, fatigue cracks are often initiated by grain boundary oxidation, and fatigue cracks often propagate along grain boundaries, where the oxidation rate is higher. Oxidation takes place at the interface between metal and gas. Properties of the metal substrate, the gaseous environment, as well as the oxides formed all interact to make the oxidation behavior of nickel-base superalloys extremely complicated. The important topics include general oxidation, selective oxidation, internal oxidation, grain boundary oxidation, multilayer oxide structure, accelerated oxidation under stress, stress-generation during oxidation, composition and substrate microstructural changes due to prolonged oxidation, fatigue crack initiation at oxidized grain boundaries and the oxidation accelerated fatigue crack propagation along grain boundaries

Selective Enzymatic Oxidation of Silanes to Silanols

Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450_(BM3) from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C−H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C−H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire

Direct methane conversion to methanol by ionic liquid-dissolved platinum catalysts

Ternary systems of inorganic Pt salts and oxides, ionic liquids and concentrated sulfuric acid are effective at catalyzing the direct, selective oxidation of methane to methanol and appear to be more water tolerant than the Catalytica reaction

In situ self cross-linking of polyvinyl alcohol battery separators

A battery separator was produced from a polyvinyl alcohol sheet structure which was subjected to an in situ, self crosslinking process by selective oxidation of the 1,2 diol units present in the polyvinyl alcohol sheet structure. The 1,2 diol units were cleaved to form aldehyde end groups which subsequently crosslink through acetalization of the 1,3 diol units of the polyvinyl alcohol. Selective oxidation was achieved using a solution of a suitable oxidizing agent such as periodic acid or lead tetraacetate

Relation between composition, microstructure and oxidation in iron aluminides

The relation between chemical composition, microstructure and oxidation properties has been investigated on various FeAl based alloys, the aim being to induce changes in the microstructure of the compound by selective oxidation of aluminium. Oxidation kinetics that was evaluated on bulk specimens showed that, due to fast diffusion in the alloys, no composition gradient is formed during the aluminium selective oxidation. Accordingly, significant aluminium depletion in the compound could be observed in the thinnest part of oxidised wedge-shape specimens. Another way to obtain samples of variable aluminium content was to prepare diffusion couples with one aluminide and pure iron as end members. These latter specimens have been characterised using electron microscopy and first results of oxidation experiments are presented

Performance of silica-supported copper oxide sorbents for SOx/NOx-removal from flue gas II. Selective catalytic reduction of nitric oxide by ammonia

The selective catalytic reduction (SCR) of nitric oxide by ammonia was studied for silica-supported copper oxide particles to be used as a sorbent/catalyst in a continuous process for the simultaneous removal of SOx and NOx from flue gases. The SCR-behaviour was determined as a function of the sulphation degree, i.e. the fraction of copper oxide converted to copper sulphate, at temperatures ranging from 20 to 450°C. Up to 350°C, the fresh catalyst with 0% CuSO4 showed a high selectivity towards production of nitrogen and water by the reaction of nitric oxide with ammonia and oxygen. At higher temperature, nitric oxide removal efficiencies decreased due to the oxidation of ammonia by oxygen. With an increase of the sulphation degree, the maximum temperature for selective catalytic reduction of nitric oxide gradually increased up to 420°C for a sulphation degree of 80%. In addition, the maximum nitric oxide removal efficiency increased as well. After regeneration of catalyst particles with a sulphation degree of 80%, realised by reduction with hydrogen and subsequent re-oxidation, the catalytic behaviour was similar to that of fresh catalyst particles with a sulphation degree of 5%. This is ascribed to the formation of some Cu2S during the reduction, which is oxidised to CuSO4 in the subsequent oxidation step. Since the selectivity towards the reduction of nitric oxide with ammonia is maintained up to about 375°C, a temperature which is very suitable for SOx removal as well, the silica-supported CuO investigated can be applied as a sorbent/catalyst for the simultaneous removal of SOx and NOx from flue gases. The reaction rate constants for SOx and NOx removal appeared to be of the same order of magnitude provided that the reduced sorbent/catalyst enters the absorber directly, i.e. without a separate pre-oxidation

Influence of reaction products on the selective oxidation of ethene

The kinetics of the selective oxidation of ethene in air over an industrial silver on ¿-alumina catalyst were studied. Special attention was paid to the influence of the reaction products on the reaction rates of epoxidation and complete combustion. Kinetic data were obtained in two different types of internal recycle reactor and in a cooled tubular reactor, and were fitted separately to several reaction rate expressions based on different kinetic models. A Langmuir-Hinshelwood mechanism, in which adsorbed ethene reacts with adsorbed molecular oxygen, was chosen as the best kinetic model. The reaction products compete for adsorption on the active sites and reduce the rates of both reactions. Carbon dioxide enhances the selectivity towards ethene oxide, whereas water has almost no influence on the selectivity. The fitting of the three individual data sets obtained in the three reactors results in accurate, but different, reaction rate expressions, whereas the fitting of the three data sets simultaneously results in less accurate reaction rate expressions. The systematic deviations found may be explained, to some extent, by differences in the operating regimes in each reactor. The main reason for the deviations is probably the different catalyst activities in the three reactors caused by poisoning. The effect of the addition of products to the feed on the behaviour of the cooled tubular reactor can be described reasonably well by a mathematical model in which the kinetic equations obtained in the laboratory reactors are incorporated. The results of these simulations are sensitive to the kinetics used