Diffusion reaction of oxygen in HfO2/SiO2/Si stacks

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.     

Ketone Catalyzed Oxidation Reactions

Dioxiranes are important oxidants for organic reactions such as epoxidation, heteroatom oxidation and oxygenation of C-H bonds. We have developed a mild and general method for epoxidation of olefins using dioxiranes generated in situ from ketones and Oxone. This method has not only extended the synthetic utility of dioxiranes, but also allowed us to discover a series of novel cyclic ketones for catalytic oxidation. In particular, we have demonstrated the potential of chiral ketones for catalytic asymmetric epoxidation of trans-olefins and trisubstituted olefins. We have also explored the potential of ketones in catalyzing oxidation of unactivated C-H bonds and decomposition of peroxynitrite.     

Efficient electrochemical conversion of carbon monoxide by rhodium octaethylporphyrin adsorbed on carbon black

We have found efficient electrocatalytic removal of CO by rhodium octaethylporphyrin on carbon black at a wide potential range. Using carbon-supported rhodium octaethylporphyrin, we have separated the Rh(II) state participating reaction and the Rh(III) state participating reaction with CO. We have clearly demonstrated electrocatalytic CO oxidation by rhodium(III) porphyrin. The onset potential for CO oxidation is much lower than that for CO oxidation by conventional Pt/Ru catalysts and cobalt porphyrin.     

碳铁催化剂的研究进展

Fe_xO_y/C复合材料作为催化剂,在有机化合物的催化氧化方面表现出非常高的活性,如对苯甲醇催化氧化苯甲醛,苯乙烯催化氧化苯甲醛,苯甲醛催化氧化苯甲酸,苯催化氧化苯酚,是最高效的催化剂之一。近年来的研究报道中,Fe_xO_y/C复合材料的制备方法主要有水热合成法,浸渍法和超声喷雾热解法。比较了三种方法各有利弊,以期寻找一种更加高效,方便,省时的制备Fe_xO_y/C复合材料的方法。其中溶液燃烧法尤为重要,溶液燃烧法给Fe_xO_y/C复合材料的制备带来了新的机遇。     

Surface immobilized optical probes: pyrene molecules covalently attached to silica and indium-doped tin oxide

We report on the covalent attachment of pyrene to quartz and indium-doped tin oxide (ITO) surfaces, and its characterization by steady-state and time-resolved emission spectroscopy. We estimate the chromophore surface coverage on the basis of their electrochemical oxidation mechanism in acidic solution. Electrochemical oxidation of immobilized pyrene results in the formation of radical cations, which are converted into hydroxypyrene and, after a second oxidation step, are transformed into isomeric forms of dihydroxypyrene/pyrenedione redox couples. Our findings demonstrate that surface-bound pyrene can be used as a spectral probe in environments that are isolated from oxidizing conditions and agents.     

The OH-initiated oxidation of 1,3-butadiene in the presence of O2 and NO: a photolytic route to study isomeric selective reactivity

We report the study of the isomeric selective OH-initiated oxidation of 1,3-butadiene in the presence of O2 and NO using the LP/LIF technique. The photolysis of monodeuterated 1-iodo-3-buten-2-ol provides only one of the possible OD-butadiene adducts, the minor addition channel product, simplifying the oxidation mechanism. We find, based on analysis of OD time-dependent traces that prompt rearrangement of initial beta-hydroxyalkyl radicals to alpha-hydroxyalkyl radicals occurs in agreement with RRKM/ME theoretical predictions. We report a rate constant of (3.3+/-1.0) x 10(-11) cm3 molecules(-1) s(-1) for deuterium abstraction from the alpha-hydroxyalkyl radical at 298 +/-2 K. Our approach demonstrates the feasibility of isomeric selective kinetic studies of the OH-initiated oxidation of unsaturated hydrocarbons.     

Active control of catalysis and product selectivity by a fuel cell system

A new concept to control catalysis and catalytic reaction through partial oxidation of alkenes with O₂ is described. Oxidation of alkenes was studied by alkene/Pd-anode/H₃PO₄-electrolyte/cathode/O₂ fuel cell (FC). An idea based on electrocatalysis and electrochemical reactions to control reaction rates and product selectivity was proposed and proven through the oxidation of propylene, Wacker and π-allyl oxidation. The oxidation rate and the product selectivity to the Wacker and the π-allyl oxidations could be controlled by changing electrode potentials. We could active control oxidation states of Pd on the anode, Pd(II) or Pd(0), during the oxidation from outer circuit. The oxidation states of Pd on the anode decided the product selectivity.     

Active control of catalysis and product selectivity by a fuel cell system

A new concept to control catalysis and catalytic reaction through partial oxidation of alkenes with O₂ is described. Oxidation of alkenes was studied by alkene/Pd-anode/H₃PO₄-electrolyte/cathode/O₂ fuel cell (FC). An idea based on electrocatalysis and electrochemical reactions to control reaction rates and product selectivity was proposed and proven through the oxidation of propylene, Wacker and π-allyl oxidation. The oxidation rate and the product selectivity to the Wacker and the π-allyl oxidations could be controlled by changing electrode potentials. We could active control oxidation states of Pd on the anode, Pd(II) or Pd(0), during the oxidation from outer circuit. The oxidation states of Pd on the anode decided the product selectivity.     

Insights into the Oxidation Chemistry of SiOC Ceramics Derived from Silsesquioxanes

We have undertaken a systematic study of the oxidation chemistry for a range of SiOC ceramics derived from silsesquioxane polymeric precursors. This study examines the oxidation for 500 hours at 600, 800, 1000 and 1200°C for four SiOC powders. The material changes upon oxidation were characterized qualitatively by color change and optical microscopy and quantitatively by weight and composition change. In this study we employ a very easy method that uses the weight change upon oxidation and a carbon analysis after oxidation to arrive at the composition of the oxidized SiOC. Combined these qualitative and quantitative techniques have shown that on oxidation at 800 and 600°C the SiOC composition is more rapidly changed to that of silica than oxidation over the same time frame at 1000 or 1200°C. The data indicates that this difference is due to the relative rates of oxidation of the excess carbon versus the Si—C bonds in the SiOC. At lower temperatures initially the carbon oxidation predominates which leads to higher porosity throughout the material and an increase in the surface area with eventually complete oxidation to silica. At higher temperatures the Si—C bond oxidation rate is comparable to the rate of oxidation of carbon. This allows a silica-like surface to build up on the SiOC, which slows all subsequent reactions due to the necessity to diffuse O2 in and COx out of the bulk. Under these oxidation conditions materials that originally contain high amounts of excess carbon are more quickly oxidized to silica than those that contain minimal amounts of excess carbon, as confirmed by elemental analysis and optical microscopy. Regardless of the time or temperature of the oxidation conditions no materials were found to be completely stable to oxidation. SiOC materials with low levels of excess carbon showed the best resistance to change upon oxidation.     

光/电化学氧化诱导C–H键官能团化

C–H键活化及其官能团化一直被认为是合成化学的圣杯,光/电氧化诱导C–H键官能团化反应为追求更为绿色、原子经济性、步骤经济性更高的现代合成化学提供了新思路.我们借助可见光或电化学氧化诱导策略实现了直接C–H键官能团化,即底物无需预官能团化,无需外加氧化剂,可直接实现碳–碳以及碳–杂键的构建.通过光/电化学氧化诱导策略使得反应在更为温和的条件下进行,能够兼容更多官能团,并且为合成化学提供一条新的途径.近些年,该策略已经应用于不同化学环境C–H官能团化构建多种化学键.本文结合该领域的代表性工作,重点介绍本课题组近些年在光/电氧化诱导C–H键官能团化反应上的研究进展,并对这一领域的前景进行了展望.     

Magnetic-field stimulated DNA oxidation

A reversible and cyclic magnetic-field stimulated DNA oxidation is described. Positioning an external magnet below the electrode attracts the DNA-functionalized magnetic particles to the surface, and stimulates the oxidation of the guanine nucleobases. Using a dual carbon-paste electrode assembly we demonstrate a spatially controlled DNA oxidation, with an `ON/OFF' switching of the electron-transfer reaction upon relocating the external magnetic field. The process can be reversed and repeated upon switching the position of the magnet, with and without oxidation signals in the presence and absence of the magnetic field, respectively. We also demonstrate a `magnetic' carbon-paste electrode, with an internal magnet, that collects the DNA-modified beads and stimulates the DNA oxidation process. The site-specific activation of the DNA oxidation holds promise for new DNA arrays and other genoelectronic applications.     

Al2O3/Au(111)反相催化剂在CO氧化反应中界面作用的理论研究

氧化物负载的金催化剂具有温和条件下优异的CO催化氧化活性。实验与理论计算表明,金与氧化物两相界面在催化反应过程中具有重要地位。反相催化剂提供了全新的角度以探究界面的重要地位。本文以Au（111）表面负载Al₂O₃团簇为反相催化剂模型,基于密度泛函理论,对催化剂模型的构型、界面性质以及O₂、CO的吸附与氧化进行了理论计算与研究。理论计算表明：电荷的迁移增强了Al₂O₃小团簇在Au（111）表面的附着,在催化剂金表面与氧化铝的两相界面位置,Au原子与Al原子的协同作用使得氧分子易于在界面位置吸附,并因此高度活化。对催化CO氧化反应路径,分别计算了缔合机理和解离机理不同路径,从活化能分析表明缔合机理比解离机理更可能发生。本文的工作揭示了反相催化剂催化CO氧化的活性本质,表明两相界面在金催化CO氧化中具有重要作用。     

SOME PREVALENT BIOMOLECULES AS DEFENSES AGAINST SINGLET OXYGEN DAMAGE

Abstract— We have compared the relative abilities of some putative biological protectors to block oxidation of 2,5-bis(hydroxymethyl)furan (BHMF)† in illuminated solutions containing the photosensitizer rose bengal and in the separated-surface-sensitizer (S-S-S) system involving pure singlet oxygen (¹ΔA_gO₂). While L-histidine is a well-known quencher of singlet oxygen, free L-histidine is not commonly found in high concentrations in nature. L-Carnosine (β-alanyl-L-histidine), however, is present in the striated muscles of many organisms, most notably mammals, in concentrations up to 40 m M . At neutral pH, carnosine quenched singlet oxygen more effectively than did equimolar histidine, both in solubilized sensitizer studies and in the S-S-S system. In the pure singlet oxygen system, 1 m M carnosine reduced the rate of BHMF oxidation as effectively as 3 m M histidine alone, or a mixture of 3 mM histidine and 3 m M β-alanine. The fungal product L-ergothioneine (2-thiol-L.-histidine betaine) and its synthetic analogue, 2-thiolhistidine, at 1 m M blocked photosensitized BHMF oxidation using solubilized rose bengal, as did urate at 0.5 m M . All three compounds failed to reduce the rate of BHMF oxidation by singlet oxygen in the S-S-S system, however. Homocarnosine (-γ-aminobutyryl-L-histidine) gave levels of protection against BHMF oxidation identical to histidine, but is present in the central nervous system only at micromolar concentrations. Neither 1 m M imidazole nor 5 m M urea reduced BHMF oxidation in either system. We conclude that some prevalent biomolecules may afford protection either by preventing singlet oxygen production (urate, L-ergothioneine) or by intercepting singlet oxygen once formed (L-carnosine). Such protective devices may be of importance in natural systems.     

The αPROX assay: fluorescence screening of the inhibitory effects of hydrophilic antioxidants on protein oxidation

We report on a new and convenient high-throughput fluorescence technique for determining antioxidant capacities of hydrophilic food samples. The new method is called αPROX (anti protein oxidation) and is based on an equimolar complex of diphenylhexatriene propionic acid (DPHPA) and bovine serum albumin (BSA) in aqueous buffer at pH 7.4. DPHPA is a reporter fluorophore that becomes nonfluorescent upon free radical-induced oxidation. In a typical assay, the DPHPA/BSA complex is challenged with peroxyl radicals and shows almost the same susceptibility to oxidation as unlabeled BSA. The progress of protein oxidation and its inhibition by antioxidants at physiological pH is determined from the time-dependent decrease in DPHPA fluorescence intensity. The αPROX method was compared to other techniques frequently used to measure antioxidant capacities. In this article, representative results are provided for the inhibitory effects of pure food components, fruit juices, wines, and various polar plant extracts on protein oxidation.      

ReaxFF reactive force field for molecular dynamics simulations of hydrocarbon oxidation

To investigate the initial chemical events associated with high-temperature gas-phase oxidation of hydrocarbons, we have expanded the ReaxFF reactive force field training set to include additional transition states and chemical reactivity of systems relevant to these reactions and optimized the force field parameters against a quantum mechanics (QM)-based training set. To validate the ReaxFF potential obtained after parameter optimization, we performed a range of NVT-MD simulations on various hydrocarbon/O2 systems. From simulations on methane/O2, o-xylene/O2, propene/O2, and benzene/O2 mixtures, we found that ReaxFF obtains the correct reactivity trend (propene > o-xylene > methane > benzene), following the trend in the C-H bond strength in these hydrocarbons. We also tracked in detail the reactions during a complete oxidation of isolated methane, propene, and o-xylene to a CO/CO2/H2O mixture and found that the pathways predicted by ReaxFF are in agreement with chemical intuition and our QM results. We observed that the predominant initiation reaction for oxidation of methane, propene, and o-xylene under fuel lean conditions involved hydrogen abstraction of the methyl hydrogen by molecular oxygen forming hydroperoxyl and hydrocarbon radical species. While under fuel rich conditions with a mixture of these hydrocarbons, we observed different chemistry compared with the oxidation of isolated hydrocarbons including a change in the type of initiation reactions, which involved both decomposition of the hydrocarbon or attack by other radicals in the system. Since ReaxFF is capable of simulating complicated reaction pathways without any preconditioning, we believe that atomistic modeling with ReaxFF provides a useful method for determining the initial events of oxidation of hydrocarbons under extreme conditions and can enhance existing combustion models.     

Investigation on the regioselectivities of intramolecular oxidation of unactivated C-H bonds by dioxiranes generated in situ

We found that dioxiranes generated in situ from ketones 1-6 and Oxone underwent intramolecular oxidation of unactivated C-H bonds at delta sites of ketones to yield tetrahydropyrans. From the trans/cis ratio of oxidation products 1a and 2a as well as the retention of the configuration at the delta site of ketone 5, we proposed that the oxidation reaction proceeds through a concerted pathway under a spiro transition state. The intramolecular oxidation of ketone 6 showed the preference for a tertiary delta C-H bond over a secondary one. This intramolecular oxidation method can be extended to the oxidation of the tertiary gamma' C-H bond of ketones 9 and 10. For ketone 11 with two delta C-H bonds and one gamma' C-H bond linked respectively by a sp(3) hydrocarbon tether and a sp(2) ester tether, the oxidation took place exclusively at the delta C-H bonds. Finally, by introducing proper tethers, regioselective hydroxylation of steroid ketones 12-14 have been achieved at the C-17, C-16, C-3, and C-5 positions.     

Experimental and Theoretical Investigations of the Existence of CuII,CuIII, and CuIV in Copper Corrolato Complexes

The most common oxidation states of copper in stable complexes are +I and +II. Cu^III complexes are often considered as intermediates in biological and homogeneous catalysis. More recently, Cu^IV species have been postulated as possible intermediates in oxidation catalysis. Despite the importance of these higher oxidation states of copper, spectroscopic data for these oxidation states remain scarce, with such information on Cu^IV complexes being non‐existent. We herein present the synthesis and characterization of three copper corrolato complexes. A combination of electrochemistry, UV/Vis/NIR/EPR spectroelectrochemistry, XANES measurements, and DFT calculations points to existence of three distinct redox states in these molecules for which the oxidation states +II, +III, and +IV can be invoked for the copper centers. The present results thus represent the first spectroscopic and theoretical investigation of a Cu^IV species, and describe a redox series where Cu^II, Cu^III, and Cu^IV are discussed within the same molecular platform.     

Characterization of Natural and Alkaline-Oxidized Proanthocyanidins in Plant Extracts by Ultrahigh-Resolution UHPLC-MS/MS

In this study, we analyzed the proanthocyanidin (PA) composition of 55 plant extracts before and after alkaline oxidation by ultrahigh-resolution UHPLC-MS/MS. We characterized the natural PA structures in detail and studied the sophisticated changes in the modified PA structures and the typical patterns and models of reactions within different PA classes due to the oxidation. The natural PAs were A- and B-type PCs, PDs and PC/PD mixtures. In addition, we detected galloylated PAs. B-type PCs in different plant extracts were rather stable and showed no or minor modification due to the alkaline oxidation. For some samples, we detected the intramolecular reactions of PCs producing A-type ether linkages. A-type PCs were also rather stable with no or minor modification, but in some plants, the formation of additional ether linkages was detected. PAs containing PD units were more reactive. After alkaline oxidation, these PAs or their oxidation products were no longer detected by MS even though a different type and/or delayed PA hump was still detected by UV at 280 nm. Galloylated PAs were rather stable under alkaline oxidation if they were PC-based, but we detected the intramolecular conversion from B-type to A-type. Galloylated PDs were more reactive and reacted similarly to nongalloylated PDs.     

Highly Selective Oxidation and Depolymerization of α,γ‐Diol‐Protected Lignin

Lignin oxidation offers a potential sustainable pathway to oxygenated aromatic molecules. However, current methods that use real lignin tend to have low selectivity and a yield that is limited by lignin degradation during its extraction. We developed stoichiometric and catalytic oxidation methods using 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as oxidant/catalyst to selectively deprotect the acetal and oxidize the α‐OH into a ketone. The oxidized lignin was then depolymerized using a formic acid/sodium formate system to produce aromatic monomers with a 36 mol % (in the case of stoichiometric oxidation) and 31 mol % (in the case of catalytic oxidation) yield (based on the original Klason lignin). The selectivity to a single product reached 80 % (syringyl propane dione, and 10–13 % to guaiacyl propane dione). These high yields of monomers and unprecedented selectivity are attributed to the preservation of the lignin structure by the acetal.     

CHARGE TRANSFER FROM PHOTOSYSTEM I TO THE CYTOCHROME b/f COMPLEX: DIFFUSION AND MEMBRANE LATERAL HETEROGENEITY

Abstract— We discuss here the minimum requirements for diffusion of a charge carrier between appressed and stroma-exposed membrane regions of chloroplasts based on recent models of the thylakoid membrane and flash-induced kinetic data. We have investigated the kinetics of the transfer of a positive charge from photosystem I to the cytochrome b/f complex in spinach chloroplasts by measuring the light-induced oxidation of cytochrome f. The rate and extent of cytochrome f oxidation were measured spectrophotometrically using either long actinic flashes that induced several turnovers of photosystem I or short actinic flashes that induced a single turnover of photosystem I. In the long actinic flashes, in the electron transfer reaction from water to methyl viologen, we observed the rapid oxidation of all of the cytochrome f present in the membrane. The half-time of the oxidation was 1.0 ± 0.1 ms. The total amount of the cytochrome was determined by chemical difference spectra to be one molecule of cytochrome f per 650 – 30 chlorophyll molecules. Using short actinic flashes we studied the photosystem I-driven electron transfer reaction from duroquinol to methyl viologen in the presence of the inhibitor 5-n-undecyl-6-hydroxy-4,7-dioxobenzothiazole. Under these conditions a single turnover flash induced the oxidation of 62 ± 5% of cytochrome f with a half-time of 240 ± 30 μs. An Arrhenius plot of the temperature dependence of the cytochrome f oxidation rate revealed an activation energy between 16 and 21 kJ/mol, a value consistent with a diffusion-controlled reaction. These kinetic data are considered in the context of two models of the thylakoid membrane.