Photoinduced Electron‐Transfer Oxidation of Olefins with Molecular Oxygen Sensitized by Tetrasubstituted Dimethoxybenzenes: A Non‐Singlet‐Oxygen Mechanism

α‐Methylstyrene ( 1 ) was photo‐oxidized in the presence of a series of alkylated dimethoxybenzenes as sensitizers in an oxygen‐saturated MeCN solution to afford the cleaved ketone 2 , epoxide 3 , as well as a small amount of the ene product 4 in ca. 1 : 1 : 0.04 ratio. The relative rate of conversion was well‐correlated with the fluorescence quantum yield of sensitizers. Thus, a non‐singlet‐oxygen mechanism is proposed, in which an excited sensitizer is quenched by (ground‐state) molecular oxygen to produce a sensitizer radical cation and a superoxide ion (O), the former of which oxidizes the substrate, while the latter reacts with the resulting olefin radical cation ( 1 ^{+ .}) to give the major oxidation products. Photodurability of such electron‐donating sensitizers is dramatically improved by substituting four aromatic H‐atoms in 1,4‐dimethoxybenzene with Me or fused alkyl groups, which provides us with an environmentally friendly, clean method of photochemical functionalization with molecular oxygen, alternative to the ene reaction via singlet oxygenation.     

Radicals Are Required for Thiol Etching of Gold Particles

Etching of gold with an excess of thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is unclear. Previous studies have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initiator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process.     

Molecular orbital calculations of the chemisorption and diffusion of oxygen and water on a graphite substrate

Semi-empirical molecular orbital calculations have been performed using the macro-molecular orbital model to simulate the chemisorption and diffusion of oxygen and water on a graphite substrate. By comparing with previous calculations of this type we have shown that the method adopted for minimising edge effects by saturating dangling carbon bonds reproduces the surface properties adequately for our purposes. Calculations using model substrates of 16 carbon and 10 hydrogen atoms and 24 carbon and 12 hydrogen atoms have been performed.The chemisorption and diffusion of oxygen has been studied by means of an equipotential contour map and the diffusion path and activation energy found. Less extensive calculations on water on graphite allow us to give a most probable diffusion path and activation energy. Sufficient results have been obtained to allow some qualitative remarks to be made on the inhibition of oxidation by an H₂O mechanism.     

Designer Lewis acid based on molecular recognition

Abstract

A Lewis acid is an excellent candidate as a proton substitute in man-made organic reactions. The observation that organoaluminum compounds immediately ignite when exposed to air, a reflection of the high affinity of aluminum for oxygen, inspired us to devise a new series of reagents based on that metal. Our goal was to engineer an artificial proton of a special shape, which could be utilized as an effective tool for chemical reactions, by harnessing the high reactivity of the aluminum atom towards oxygen. Such a concept was initially researched by examining the influence of a specially designed organometallic reagent on a typical organic reaction. The successful diastereoface discrimination observed in the alcohol synthesis induced us to examine the more intricate question of enantioface differentiation. Creation of new chirality in a product molecule requires the use of a chiral catalyst. Therefore, an investigation was launched to determine whether a chiral Lewis acid could possibly achieve the desired result.     

Mo(Tm(Me))(O)2Cl]: an alternative functional model of sulfite oxidase

The hydrotris(methimazolyl)borate anion (TmMe) has been used to synthesize an alternative functional model ([Mo(TmMe)(O)2Cl]) of the metalloenzyme sulfite oxidase. It has been shown that the complex undergoes oxygen atom transfer chemistry and that it performs the primary function of the enzyme, sulfite oxidation. A method using ion chromatography has been developed to definitively prove that sulfite is oxidized to sulfate. Employment of a soft tripodal ligand has allowed us to tune the redox potentials of our complex so that they are significantly closer to those reported for sulfite oxidase.     

Kinetic Monte Carlo simulations of oxygen vacancy diffusion in a solid electrolyte: Computing the electrical impedance using the fluctuation–dissipation theorem

We present a new method for computing the electrical impedance of solid oxide electrolyte from kinetic Monte Carlo simulations of oxygen vacancy diffusion. The impedance values at all frequencies are obtained from a single equilibrium simulation based on the fluctuation–dissipation theorem, leading to a significant gain of efficiency over existing methods.This allows us to systematically examine the effect of dopant concentration. Increasing dopant concentration is found to decrease the infinite-frequency impedance, which is attributed to the increasing density of oxygen vacancies. The difference between the impedance values at zero- and infinite-frequency, on the other hand, shows the opposite trend, and is linked to dopant–vacancy interactions. Hence the two competing mechanisms, previously proposed to explain the existence of an optimal doping concentration, are separately quantified.Our model also predicts a significant effect of the arrangement of dopant cations on the electrolyte conductivity.     

Heteronuclear NOE spectroscopy of ionic liquids

(19)F,(1)H HOESY experiments with three ionic liquids ([bmim]BF(4), [bmim]PF(6) and [emim]BF(4)) were run in two different solvents and neat. The results give preferred probabilities of presence and enable us to systematically study interactions between the cations and the anions in the ionic liquid phase by NMR spectroscopy. The influence of different solvents and of the presence or absence of air (i.e. oxygen) is discussed. This enabled us to substantially speed up the NMR experiments and to develop a more precise method for the investigation of liquid-phase structures in ionic liquids.     

Extension of the modified Sanderson method to ternary mixed oxides derived from hydrotalcite-like compounds and its correlation to CO2 (TPD-CO2) desorption peak maxima

A simple, intuitive and computationally non-intensive modified model, proposed first for the prediction of the catalyst basicity of binary mixed oxides, based simply on the chemical composition using the Sanderson Method was extended to ternary systems. The modification of the method allows the discrimination between the oxygen charge on different chemical environments (differences between local and global composition). TPD-CO₂ result was used to the validation between theoretical values and experimental results, letting us propose a correlation between the oxygen charge of the different clusters and the TPD-CO₂ peak maxima.     

Thermal Oxidation of Carbonaceous Nanomaterials Revisited: Evidence of Mechanism Changes

Kinetic data, for example, activation energy and reaction order, are crucial for the understanding of chemical reactions and processes. Here, we describe a novel method for obtaining kinetic data based on thermogravimetric measurements (TGA) that exploits in each measurement multiple successive isothermal steps (SIS). We applied this method to the notoriously challenging carbon combustion process for vastly different carbons for oxygen molar fractions between 1.4 % and 90 %. Our obtained apparent E_A values are within the wide range of results in the literature and vary in a systematic way with the oxygen partial pressure. The improved accuracy and large amount of obtainable data allowed us to show that the majority of experimentally obtained apparent data for apparent E_A are neither in a kinetic regime nor in a diffusion‐controlled one but rather in a transition regime.     

Design variations of a polymer–enzyme composite biosensor for glucose: Enhanced analyte sensitivity without increased oxygen dependence

The glucose sensitivity and oxygen dependence of a variety of implantable biosensors based on glucose oxidase (GOx), incorporating an electrosynthesized poly-o-phenylenediamine (PPD) permselective barrier on 125-μm diameter Pt disks (Pt_D) and cylinders (Pt_C, 1-mm length), were measured and compared. Full glucose calibrations and experimental monitoring of solution oxygen concentration allowed us to determine apparent Michaelis–Menten parameters for glucose and oxygen. In the linear region of glucose response, the most sensitive biosensor design studied was Pt_D/PPD/GOx (enzyme deposited over polymer) that was 20 times more sensitive than the more widely used Pt_C/GOx/PPD (enzyme immobilized before polymer deposition) configuration. The oxygen dependence, quantified as K_M(O₂), of both active and less active designs was surprisingly similar, a finding that could be rationalized in terms of an increase in K_M(G) with increased enzyme loading. The Pt_D/PPD/GOx design will now enable us to explore glucose concentration dynamics in smaller and layered brain regions with good sensitivity and minimal interference from fluctuations in tissue pO₂.     

PRIMARY MECHANISMS OF ERYTHROCYTE PHOTOLYSIS INDUCED BY BIOLOGICAL SENSITIZERS AND PHOTOTOXIC DRUGS

Abstract— The elucidation of the molecular mechanism of photosensitized hemolysis of red blood cells may give important clues to the primary events underlying the phototoxic reactions observed in pathological conditions such as porphyria and induced by photosensitizing drugs. Sensitizers effective in photo-hemolysis are porphyrins, the tryptophan metabolite kynurenic acid, and phototoxic drugs such as chlor-promazine and demethylchlortetracycline. Utilizing the singlet oxygen quenchers. jS-carotene and histi-dine and the large deuterium effect on the lifetime of singlet oxygen previously described by us, good evidence of the participation of this excited molecular species in the photohemolysis in the presence of kynurenic acid was obtained. Chlorpromazine and demethylchlortetracycline clearly act by a non-singlet oxygen pathway. The situation observed with haematoporphyrin is less clear and may represent a mixed Type I-Type II mechanism.     

The effect of an aminoalcohol on the polymerization of acrylates with type II initiators

In this study, the authors report the use of an aliphatic amine and an aromatic aminoalcohol as synergists with various Type II initiators by using Photo-DSC (Photo-differential scanning calorimetry) technique. The photopolymerization of triacrylate and diacrylate was performed under nitrogen atmosphere in the presence of an amine or aminoalcohol with type II initiators, which allowed us to compare the efficiency of the initiating radicals. The oxygen scavenging role of the amine was left out.     

In situ oxidation study of Pt(110) and its interaction with CO

Many interesting structures have been observed for O(2)-exposed Pt(110). These structures, along with their stability and reactivity toward CO, provide insights into catalytic processes on open Pt surfaces, which have similarities to Pt nanoparticle catalysts. In this study, we present results from ambient-pressure X-ray photoelectron spectroscopy, high-pressure scanning tunneling microscopy, and density functional theory calculations. At low oxygen pressure, only chemisorbed oxygen is observed on the Pt(110) surface. At higher pressure (0.5 Torr of O(2)), nanometer-sized islands of multilayered α-PtO(2)-like surface oxide form along with chemisorbed oxygen. Both chemisorbed oxygen and the surface oxide are removed in the presence of CO, and the rate of disappearance of the surface oxide is close to that of the chemisorbed oxygen at 270 K. The spectroscopic features of the surface oxide are similar to the oxide observed on Pt nanoparticles of a similar size, which provides us an extra incentive to revisit some single-crystal model catalyst surfaces under elevated pressure using in situ tools.     

Study of Products of the Alkaline Decomposition of Hydrolysis Lignin by Atmospheric Pressure Photoionization High-Resolution Mass Spectrometry

A method of high resolution-mass spectrometry with acetone doped atmospheric pressure photoionization was used to study products of the alkaline solvolysis of hydrolysis lignin. It was found that the mass spectrum of the depolymerization products of hydrolysis lignin consists of about seven thousand peaks of oligomers, containing up to 10 aromatic units with an average molecular weight of 150 Da. Calculations of the elemental compositions of all detectable oligomers and their visualization on the van Krevelen coordinates allowed us to show that the studied sample differs from native (virgin released) lignin by the presence of fractions with high oxygen contents and highly unsaturated condensed structures, including polynuclear aromatic hydrocarbons. The structural units of lignin oligomers were characterized using an approach based on the collision induced dissociation of precursor ions in a broad m/z range.     

混合控制下腐蚀过程的电化学动力学参数测定

通过恒电量脉冲技术测定Q235碳钢在天然海水中腐蚀过程的电化学动力学参数. 分别利用不同极化幅度的恒电量瞬态响应分析获得极化电阻和Tafel斜率, 进而计算腐蚀电流icorr. 并对比了恒电量方法和考虑扩散影响的稳态极化曲线方法的测量结果. 结果表明, 采用恒电量强极化积分算法(CPSI)获得的Tafel斜率与极化曲线方法有很好的相关性. 同时, CPSI测定的阴极Tafel斜率符合氧还原反应的理论Tafel斜率值. 因此, 采用恒电量瞬态响应测量大大减小了浓差极化的影响, 有利于快速测定电荷传递和扩散传质混合控制下腐蚀过程的电化学动力学参数.     

Chemically bonded graphene/BiOCl nanocomposites as high-performance photocatalysts

After the successful solvothermal synthesis of graphene (GR) from ethanol and sodium, we obtained chemically bonded graphene/BiOCl (GR/BiOCl) nanocomposite photocatalysts via a facile chemical-bath method. A significant enhancement was observed in the photodegradation of methylbenzene, which was largely ascribed to the chemical coupling effects between Bi and C, as shown by X-ray photoelectron spectroscopy. Raman spectroscopy also indicated an increased size of the sp(2) ring clusters and decreased disorder in the graphitic structure, as substitutions of defects like vacancies as well as oxygen containing carbonaceous groups with C-Bi attachment take place. Overall, information about chemical coupling effects between GR and BiOCl might take us a step further in GR-based hybrid materials, providing a very good reference to the fabrication of chemically bonded GR/semiconductor compounds and facilitating their applications in environmental protection, photo-electrochemical conversion and photocatalytic decomposition of water.     

Effect of Preparation Method on the Structural Characteristics of NiO-ZrO2 Oxygen Carriers for Chemical-looping Combustion

Chemical-looping combustion(CLC) offers an effective approach for power generation and CO₂ capture. In this work, an NiO-ZrO₂ oxygen carrier prepared by three methods was subjected to an optimal reaction temperature test, an optimal flow test and a cyclic redox reaction test to explore the most suitable reaction conditions. Through comparative analysis, it is noted that the coprecipitation method is not suitable for the preparation of this NiO-ZrO₂ oxygen carrier, while the oxygen carrier prepared by the mechanical mixing method and solution combustion method obtained a higher CH₄ conversion rate and CO₂ selectivity. In addition, these two oxygen carriers also showed high stability during successive CLC testing. Therefore, both the mechanical mixing method and the solution combustion method can be used to prepare NiO-ZrO₂ oxygen carriers.     

First kinetic discrimination between carbon and oxygen reactivity of enols

Nitrosation of enols shows a well-differentiated behavior depending on whether the reaction proceeds through the carbon (nucleophilic catalysis is observed) or the oxygen atom (general acid-base catalysis is observed). This is due to the different operating mechanisms for C- and O-nitrosation. Nitrosation of acetylacetone (AcAc) shows a simultaneous nucleophilic and acid-base catalysis. This simultaneous catalysis constitutes the first kinetic evidence of two independent reactions on the carbon and oxygen atom of an enol. The following kinetic study allows us to determine the rate constants for both reaction pathways. A similar reactivity of the nucleophilic centers with the nitrosonium ion is observed.     

Efficient surface grafting of luminescent silicon quantum dots by photoinitiated hydrosilylation

We suggest a method for efficient (high-coverage) grafting of organic molecules onto photoluminescent silicon nanoparticles. High coverage grafting was enabled by use of a modified etching process that produces a hydrogen-terminated surface on the nanoparticles with very little residual oxygen and by carefully excluding oxygen during the grafting process. It had not previously been possible to produce such a clean H-terminated surface on free silicon nanoparticles or, subsequently, to produce grafted particles without significant surface oxygen. This allowed us to (1) prepare air-stable green-emitting silicon nanoparticles, (2) prepare stable dispersions of grafted silicon nanoparticles in a variety of organic solvents from which particles can readily be precipitated by addition of nonsolvent, dried, and redispersed, (3) separate these nanoparticles by size (and therefore emission color) using conventional chromatographic methods, (4) protect the particles from chemical attack and photoluminescence quenching, and (5) provide functional groups on the particle surface for further derivatization. We also show, using 1H NMR, that the photoinitiated hydrosilylation reaction does not specifically graft the terminal carbon atom to the surface but that attachment at both the first and second atom occurs.     

Influence of the hydrodynamics on the biofilm formation by mass transport analysis

Biofilm are formed wherever there is some water in our environment: pipes, pipelines, tap water systems, air conditioning systems... Furthermore, the ecological and economical consequences are very important: energy losses, bacterial contamination, material deterioration. The aim of this work is to develop a new method to detect and monitor the biofilm formation. This method can also determine some mechanical properties of the biofilm. An application of this method is a realization of a biofilm sensor. Biofilm is considered as an inert porous layer with respect to mass transport. In our experiment, the biofilm is grown on a gold electrode in natural seawater. Its thickness is determined by considering the oxygen diffusion limiting current measured for different rotation speeds on this electrode. Two different incubators are used during the biofilm development: one, with a laminar flow, permits the rotation of the electrode during the biofilm formation, and for the second, a tube is used under turbulent conditions during the biofilm formation. This experiment allows us to characterize the mechanical behavior (thickness, elasticity, rigidity) of the biofilm in function of different conditions of development.