The Chemistry of DPPH· Free Radical and Congeners

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH^·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Milk from cows fed a diet with a high forage:concentrate ratio improves inflammatory state,oxidative stress,and mitochondrial function in rats

Excessive energy intake may evoke complex biochemical processes characterized by inflammation, oxidative stress, and impairment of mitochondrial function that represent the main factors underlying noncommunicable diseases. Because cow milk is widely used for human nutrition and in food industry processing, the nutritional quality of milk is of special interest with respect to human health. In our study, we analyzed milk produced by dairy cows fed a diet characterized by a high forage:concentrate ratio (high forage milk, HFM). In view of the low n-6:n-3 ratio and high content of conjugated linoleic acid of HFM, we studied the effects of this milk on lipid metabolism, inflammation, mitochondrial function, and oxidative stress in a rat model. To this end, we supplemented for 4 wk the diet of male Wistar rats with HFM and with an isocaloric amount (82 kJ, 22 mL/d) of milk obtained from cows fed a diet with low forage:concentrate ratio, and analyzed the metabolic parameters of the animals. Our results indicate that HFM may positively affect lipid metabolism, leptin:adiponectin ratio, inflammation, mitochondrial function, and oxidative stress, providing the first evidence of the beneficial effects of HFM on rat metabolism.     

氧化还原功能纤维的研究 Ⅷ．含正丙胺基吸附剂与Au~（3＋）的氧化还原反应机理

通过元素分析、红外光谱分析、光电子能谱分析以及扫描电子显微镜分析等手段，证实含正丙胺基吸附剂与Ａｕ３＋的氧化还原反应过程中，氮原子邻近的羟基碳或Ｃ－Ｈ键被氧化，而氮原子并未参与氧化还原反应；吸附态Ａｕ（３＋）最终部分被还原成单质金；在非水介质中吸附在吸附剂上的金聚集成颗粒状。     

磷酸盐激光玻璃中铂颗粒密度与氧化还原平衡关系的研究

用吸收光谱法研究了Ｒ２Ｏ—ＢａＯ—Ｐ２Ｏ５系统磷酸盐激光玻璃中铂颗粒密度与铭的氧化还原平衡的关系。结果表明，玻璃中铂颗粒密度随平衡向右移动而减小；玻璃中平衡随熔炼气氛中氧分压增大、熔炼温度升高而向右移动，当足够大时，铂颗粒不能形成。     

新型VAE乳液及其在胶粘剂中的应用

介绍了在高压环形反应器上采用连续聚合工艺进行的VAE(醋酸乙烯-乙烯共聚物)乳液新品种的开发。通过在普通型VAE乳液配方基础上调整保护胶体的品种和用量,并采用新型氧化-还原引发体系,生产出高固含(6S%)低粘度的VAE乳液,具有优异的粘接强度和干燥速度。用于包装行业的快速粘接和配制成木材拼板胶,效果优异。     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

Automated fluorimetry in quality control of pasteurized and ultra-high temperature-treated starch soup

Automated monitoring of the microbiological quality of heat-processed foods by the resazurin reduction test was applied to microtitration plate incubator-fluorimeter technology. The appearance and disappearance of the fluorescing peak of resorufin was monitored on microtitration trays. Pasteurized or ultra-high temperature-treated starch-based soup was used as the model food system. Bacillus subtilis spores (ultra-high temperature treatment) and vegetative cells of Enterococcus faecalis (pasteurization) were inoculated into the soup before the heat treatment at levels which resulted in some survival. The timing of appearance of maximum fluorescence correlated with the number of bacteria in pre-incubated samples. Automated resazurin-reduction fluorimetry was compared with conventional plating, turbidometry and microcolony count by the direct epifluorescent filter technique. The results of the resazurin test correlated well with those of all the other methods tested. Fluorimetry had the advantage that the results could be read within 1–5h and the reproducibility was superior to the other methods.     

Iodide mediated electrolysis of acidic coke/coal suspension

Hydrogen is among the emerging energy vectors that are being developed to replace nonrenewable hydrocarbon energy sources. The preferred method to produce hydrogen without generating greenhouse gases is the electrolysis of water using renewable energy. The reduction of energy during the water electrolysis process is a desirable goal regardless of the source of electric power. Similar to ferrous/ferric mediation, iodide can be used as a mediator in the electrolysis of an acidic suspension of coke or coal. The iodide ion is oxidized at a far lower anodic potential than the alternative oxygen evolution reaction. This reduces the cell electrolysis voltage and, consequently, reduces electricity use. The iodide consumed at the anode is continuously regenerated by chemical reaction with the coke/coal in suspension.     

Effect of functional group of ferrocene redox substance on the transport properties of newly designed ion exchange membrane prepared from polymer gel

A different newly designed cationic exchange polymer membrane and anionic exchange polymer membrane were introduced, and also the transport properties of these polymeric membranes were investigated in this study. The transport properties of these polymer membranes in contact with ferrocene redox derivatives were estimated by using electrochemical techniques such as cyclicvoltammetry, chronopotentiometry, and chronoamperometry techniques, respectively. The used ferrocene redox substances, which have different functional groups, were (Ferrocenylmethyl) trimethylamonium iodide, FcMA, Ferrocenedimethanol, FcDM, and Ferrocene carboxylic acid, FcCA. It indicated that the performance of a membrane depended on the content of polymer gel, anionic exchange polymer site (20 wt % and 50 wt %) or cationic polymer exchange site (20 wt % and 50 wt %), and the efficiency of the functional groups of cationic and anionic exchange polymer site as well. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008