超声空化状态对苯酚降解的影响

给出不同空化状态下超声波降解苯酚溶液的实验结果,比较了相应的声压级频谱和合成声强。研究了苯酚溶液的浓度,二阶铁盐,超声辐射时间对苯酚降解率的影响,讨论了不同空化状态下的声压级频谱特征。     

New materials with high π conjugation by reaction of 2-oxazoline containing phenols with polyamidines and inorganic base

The non-covalent interactions between 2-oxazoline containing phenols and an aliphatic polyamidines as well as an inorganic base were studied. The reaction of a weak acid with a strong base results in the formation of the deprotonated species and subsequently in the formation of a new electronic structure. A bathochromic shift of the wavelength of the absorption maxima of the chromophores bounded to polyamidine was observed. Depending on the structure of the chromophore, the shift of the absorption maxima is 40-100 nm. The changes in photochemical behavior can be explained by the higher portion of quinoid structures in the conjugated π-system. The degree of deprotonation is dependent on the molar ratio of the chromophore and the polymeric base. Analogous results were obtained with an inorganic base.     

H2O2在苯酚降解过程中的作用研究

H2O2浓度是影响苯酚降解程度的重要因素之一。实验表明,不同浓度的H2O2在苯酚降解过程中所起的主要作用也不相同。在环状有机物的降解过程中,苯酚往往作为副产物出现,因此,苯酚的降解程度也往往影响到这些环状有机物的降解程度。H2O2在光氧化、光催化氧化和光电催化氧化的条件下均能影响苯酚的降解程度。在后两种条件下,H2O2还影响到用作光催化剂的TiO2的活性。     

Selective Electrochemical Hydrogenation of Phenol with Earth-abundant Ni−MoO2 Heterostructured Catalysts: Effect of Oxygen Vacancy on Product Selectivity

Herein, we report highly efficient carbon supported Ni−MoO₂ heterostructured catalysts for the electrochemical hydrogenation (ECH) of phenol in 0.10 M aqueous sulfuric acid (pH 0.7) at 60 °C. Highest yields for cyclohexanol and cyclohexanone of 95 % and 86 % with faradaic efficiencies of ∼50 % are obtained with catalysts bearing high and low densities of oxygen vacancy (O_v) sites, respectively. In situ diffuse reflectance infrared spectroscopy and density functional theory calculations reveal that the enhanced phenol adsorption strength is responsible for the superior catalytic efficiency. Furthermore, 1-cyclohexene-1-ol is an important intermediate. Its hydrogenation route and hence the final product are affected by the O_v density. This work opens a promising avenue to the rational design of advanced electrocatalysts for the upgrading of phenolic compounds.     

Studies of Phenol Electrooxidation Performed on Platinum Electrode in Dimethyl Sulphoxide Medium. Determination of Unreacted Phenol by the Effect of 4-Vinylbenzenesulphonate on the Electrooxidation Process

The electrooxidation of phenol was studied in the presence of sodium 4-vinylbenzenesulfonate in various quantities. When the sulphonate was dissolved in equal or higher quantities than phenol the peak currents increased gradually and suppression of electropolymerization was observed. When the sulphonate quantity was smaller than that of phenol brown films fouled the electrode. The observed phenomenon was utilized in an analytical procedure namely determination of unreacted phenol in electrolysis solution with linear dynamic range between 0 and 50 mM and 2.96 mM detection limit. The shape of curve became saturated-like above 50 mM.     

A De Novo-Designed Type 3 Copper Protein Tunes Catechol Substrate Recognition and Reactivity

De novo metalloprotein design is a remarkable approach to shape protein scaffolds toward specific functions. Here, we report the design and characterization of Due Rame 1 (DR1), a de novo designed protein housing a di-copper site and mimicking the Type 3 (T3) copper-containing polyphenol oxidases (PPOs). To achieve this goal, we hierarchically designed the first and the second di-metal coordination spheres to engineer the di-copper site into a simple four-helix bundle scaffold. Spectroscopic, thermodynamic, and functional characterization revealed that DR1 recapitulates the T3 copper site, supporting different copper redox states, and being active in the O₂-dependent oxidation of catechols to o-quinones. Careful design of the residues lining the substrate access site endows DR1 with substrate recognition, as revealed by Hammet analysis and computational studies on substituted catechols. This study represents a premier example in the construction of a functional T3 copper site into a designed four-helix bundle protein.