Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide

[PW₁₁ZnO₃₉]^5? was immobilized on activated carbon and characterized using Fourier transform infrared, X‐ray diffraction, Brunauer–Emmett–Teller and elemental analysis techniques. Effective oxidation of various alcohols with hydrogen peroxide was performed in the presence of this catalyst. Easy separation of the catalyst from the reaction mixture, cheapness, high activity and selectivity, stability as well as retained activity in subsequent catalytic cycles make this supported catalyst suitable for small‐scale synthesis. Copyright © 2015 John Wiley & Sons, Ltd.     

对位酚类衍生物作为化学发光分析的增强剂研究

在化学发光分析中，常常要用到碱性条件下鲁米诺与过氧化氢的反应系统，通过催化剂辣根过氧化物酶使反应顺利进行。如果再加入适当的增强剂，则灵敏度提高且发光时间延长，可改善测定的重现性。实验证明，对位酚类衍生物，如：对叔丁基苯酚，对甲苯酚的发光增强作用明显，其发光效率可上升几十倍，发光时间也获得有效延长。     

Indirect Oxidation of Organic Substances by Intermediates of the Oxygen Reduction

Results of two urgent and practically important directions of research on the indirect oxidation of organic compounds by highly reactive intermediates generated electrochemically from oxygen (HO₂ ^–, HO₂ ^·, HO^·) are considered and orderly arranged. The studies in question are the indirect synthesis and mineralization of organic toxicants in waste water.     

An N,N′-diaryl urea based conjugated polymer model system

An N,N′-diphenyl urea was designed as a model system for aggregation phenomenon in poly(phenyleneethynylenes) (PPEs). The unmethylated N,N′-diphenyl urea adopts an open, unfolded conformation in which the two diphenyl acetylene fluorophores are far enough away, mimicking the unaggregated state. Dimethylation forces the aromatic surfaces together into π-π contact, mimicking the aggregated state of PPEs. Analogous to bulk PPEs, this model system shows dramatic differences in quantum yield between the folded and unfolded states, with the unfolded urea having greater than 400-fold higher fluorescence quantum yield than its folded equivalent.     

1H and 13C NMR spectroscopic study of oxidation of D,L‐cystine and 3,3′‐dithiobis(propionic acid) with hydrogen peroxide in aqueous solution

The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D₂O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu²⁺ cations, but not Fe³⁺ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.     

Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

Catalysis by Ir(III), Rh(III) and Pd(II) metal ions in the oxidation of organic compounds with H2O2

Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H₂O₂. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine and (±)-convolutamydines A and E, through enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones

Claisen rearrangement triggered by enolization of 2-allyloxyindolin-3-ones with DBU was performed in order to prepare 3-allyl-3-hydroxyindolin-2-ones. Total synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine, as well as (±)-convolutamydines A and E, was achieved by transformation of the allyl moiety of 3-allyl-3-hydroxyindolin-2-ones.