Organofluorine Hydrazone Derivatives as Multifunctional Anti-Alzheimer's Agents with CK2 Inhibitory and Antioxidant Features

A set of novel hydrazone derivatives were synthesized and analyzed for their biological activities. The compounds were tested for their inhibitory effect on the phosphorylating activity of the protein kinase CK2, and their antioxidant activity was also determined in three commonly used assays. The hydrazones were evaluated for their radical scavenging against the DPPH, ABTS and peroxyl radicals. Several compounds have been identified as good antioxidants as well as potent protein kinase CK2 inhibitors. Most hydrazones containing a 4-N(CH₃)₂ residue or perfluorinated phenyl rings showed high activity in the radical-scavenging assays and possess nanomolar IC₅₀ values in the kinase assays.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

Non-invasive headspace measurement for characterizing oxygen-scavenging in polymers

A non-invasive headspace analysis method to measure rate and amount of oxygen uptake in oxygen-scavenging polymers is presented. Oxygen uptake data for metal-catalyzed poly(1,4-butadiene) at 30 °C are provided to illustrate the method. These data were obtained by measuring oxygen headspace concentration above the scavenging polymer with an OxySense^® 200T non-invasive oxygen sensor, and, for comparison, oxygen uptake was measured with an analytical balance. Excellent agreement was observed between these two independent experiments.     

Study of the coupling reactions between electrochemically generated aromatic radical anions and methyl, alkyl and benzyl radicals

Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×10⁹ M⁻¹ s⁻¹. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an S_N2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such S_N2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 10⁹ M⁻¹ s⁻¹.     

冬凌草硒多糖的制备、表征及抗氧化活性分析

本研究以济源冬凌草多糖为原料，选用化学合成方法对多糖进行结构修饰。采用UV、FT-IR、SEM、TGA、HPLC等方法对冬凌草多糖以及硒多糖结构特征进行了表征；通过DPPH（1,1-二苯基-2-三硝基苯肼）自由基法、羟自由基法等4种方法对其抗氧化活性进行了探究。结果：制备的硒多糖中硒质量分数为1.35 mg/g。硒化修饰后，冬凌草多糖的基本骨架得到保留，单糖种类未发生改变，但其分解温度降低、稳定性下降，多糖形貌也发生明显变化，球状与条状形貌增多，片状形貌减少。此外，在体外抗氧化性实验中，当硒多糖质量浓度为1.6mg/mL时，对DPPH自由基、ABTS自由基、羟自由基清除率分别为68.68%、86.69%、45.12%，均强于冬凌草多糖。     

Improved oxidative stability of sunflower oil in the presence of an oxygen-scavenging film

The oxidative stability of sunflower oil (SFO) was measured during storage at 23 and 37°C in the presence of a novel oxygen-scavenging film that contained polyfuryloxirane (PFO). Commercially refined and deodorized SFO was stored in a lighted room in sealed transparent packages containing either PFO film or an antioxidant, 0.02% butylated hydroxytoluene (BHT). Oxidative stability was evaluated by determination of peroxide values and gas-chromatographic measurement of headspace hexanal. SFO stored in the presence of the oxygen-scavenging film was more stable than oil stored without the film, or than film stored with 0.02% BHT. The PFO film scavenges oxygen through energy-transfer sensitization of singlet oxygen. The film is doped with eosin and the naturally-occurring dye, curcumin, which absorb over a wide range of visible wavelengths. Curcumin transfers its absorbed energy to eosin, which sensitizes the production of singlet oxygen. The singlet oxygen is scavenged by PFO. The use of two dyes increases the efficiency of the sensitization process, reducing the illumination time and intensity required for effective oxygen scavenging.     

Radical scavenging activity of canola hull phenolics

Possible use of canola hulls as a source of natural anti-oxidants was explored. Cyclone canola hulls were extracted with methanol (30 to 80%, vol/vol) and acetone (30 to 80%, vol/vol). The free radical-scavenging activity of phenolic extracts so prepared was evaluated using the 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonate) (ABTS) radical ion (ABTS^o−), 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, and chemiluminescence assays. The total content of phenolics in prepared extracts from canola hulls ranged from 15 to 136 mg sinapic acid equivalents per gram of extract. Higher levels of condensed tannins were detected in the acetone extracts than in the corresponding methanolic counterparts. Seventy and 80% (vol/vol) acetone extracts displayed markedly stronger antioxidant activity than any of the other extracts investigated. Statistically significant linear correlations were found between TEAC (Trolox equivalent antioxidant capacity) values (expressed in mM of Trolox equivalents per gram of extract) and total pehnolics, TEAC and total condensed tannins (i.e., determined using the modified vanillin and pronthocyanidin assays), as well as TEAC and protein precipitation activity of phenolic extracts (i.e., measured using the dye-labeled assay). The antioxidant activities of extracts as determined by the ABTS^o− radical ion assay correlated highly with those of the chemiluminescence and DPPH radical assays.     

Glyoxal Ozonation Process in Aqueous Solution

The process of ozonation of glyoxal in aqueous solution has been studied by following its chemical and kinetic evolution. Results show that the oxidative process leads to formation of carboxylic functions and carbon dioxide according to a constant selectivity ratio at varying conversion degree.. Comparison between the oxygen amounts of reaction products and the corresponding ozone consumptions reveals that molecular oxygen takes part in the reaction process. System behavior is explained on the basis of radical reaction mechanism.     

Observations on the estimation of scavenging activity of phenolic compounds using rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH<Superscript>•</Superscript>) tests

Rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH^•) tests are often applied to classify the scavenging activity of phenolic compounds (AH). Published analytical protocols differ in more than one experimental condition, and results for the relative order or magnitude of activity are often contradictory. In this work, parameters such as duration of test, [AH]/[DPPH^•] molar ratio, and solvent effects were examined and discussed. The test duration and the value of the [AH]/[DPPH^•] ratio did not influence the order of activity among tested antioxidants. Ethanol, commonly used as solvent in such tests, was compared with acetonitrile and tert-butyl alcohol. Solvent properties such as the ability to form hydrogen bonds with the AH seem to influence the level of the relative activity (%RSA). Higher %RSA values were observed in ethanol. The activity of the most polar compounds was affected the most, and in some cases (caffeic, dihydrocaffeic, and rosmarinic acids) the order of activity was changed owing to different kinetics. Standardization of the analytical protocol should include a 20-min reaction period and a molar ratio that permits attainment of a 60–80% RSA value for the most potent antioxidant. Solvent choice is critical for classifying activity. Safe classification can be based only on results from kinetic studies.