AN AB INITIO STU DY ON THE CORELATION BETWEEN THE ABSOLUTE CONFIGURATION AND THE CD SPECTRA OF ORGANIC PEROXIDES

Correlation between the absolute configuration and the CD spectra of organic peroxides was studied by ab initio method with a mo- d el moleeule CH_3-O-O-CH_3.For P form when 0°≤θ(twist angle of C-O-O-C) <90°, there is positive Cotton effect;when 90°<θ≤180°, there is nega- tive Cotton effect;the curve is bisignate at θ=90°.

STUDIES ON THE INITIATION MECHANISM OF ORGANIC PEROXIDE AND N-METHACRYLOYLOXYETHYL-N-METHYL ANILINE IN METHYL METHACRYLATE POLYMERIZATION

The initiation mechanism of methyl methacrylate (MMA) polymerization by organic peroxide and polymerizable aromatic tertiary amine such as N-methacryloyloxyethyl-N-methyl aniline (MEMA) binary system has been studied. The kinetics of polymerization of MMA and the ESR spectra of organic peroxide/MEMA system were determined. Based on the ESR study and the end-group analysis by UV spectra of the polymer formed, the initiation mechanism is proposed.

Adiabatic Decomposition of Two Kinds of Organic Peroxides by Accelerating Rate Calorimeter

The accelerating rate calorimeter was applied to study the thermal hazard of two kinds of organic peroxides, i.e. methyl ethyl ketone peroxide (MEKPO) and benzoyl peroxide (BPO). And their thermal decomposition characteristics were discussed. Meanwhile, thermal decomposition characteristics of MEKPO and BPO vvere compared. The result indicated that MEKPO is more sensitive to thermal effect than BPO. While once the thermal decomposition takes place. BPO will be more hazardous than MEKPO due to its serious pressure effect. Thermal kinetic analysis of these two kinds of organic peroxides was also taken, and the kinetic parameters for them were calculated. The study of thermal decomposition of MEKPO solution with different initial concentrations indicated that, the lower concentration MEKPO solution is, the higher onset temperature will be. And with the addition of organic solvent, it becomes more difficult for MEKPO to reach a thermal decomposition. Therefore, its thermal hazard is reduced.

Estimation of thermal decomposition temperatures of organic peroxides by means of novel local and global descriptors

The thermal decomposition temperature is one of the most important parameters to evaluate fire hazard of organic peroxide. A quantitative structure-property relationship model was proposed for estimating the thermal decomposition temperatures of organic peroxides. The entire set of 38 organic peroxides was at random divided into a training set for model development and a prediction set for external model validation. The novel local molecular descriptors of AT1, AT2, AT3, AT4, AT5, AT6 and global molecular descriptor of ATC have been proposed in order to character organic peroxides’ molecular structures. An accurate quantitative structure-property relationship （QSPR） equation is developed for the thermal decomposition temperatures of organic peroxides. The statistical results showed that the QSPR model was obtained using the multiple linear regression （MLR） method with correlation coefficient （R）, standard deviation （S）, leave-one-out validation correlation coefficient （RCV） values of 0.9795, 6.5676 ℃ and 0.9328, respectively. The average absolute relative deviation （AARD） is only 3.86% for the experimental values. Model test by internal leave-one-out cross validation and external validation and molecular descriptor interpretation were discussed. Comparison with literature results demonstrated that novel local and global descriptors were useful molecular descriptors for predicting the thermal decomposition temperatures of organic peroxides.

STUDIES ON ORGANIC PEROXIDE/N, NDI(2-α-METHYL-ACRYLOYLOXY PROPYL)-PARA-TOLUIDINE BINARY SYSTEMS

The polymerization of methyl methacrylate (MMA) initiated by organic peroxide and polymerizable aromatic tertiary amine such as N, N-di (2-α-methylacryloyloxy propyl)-p-toluidine (MP)_2PT binary system has been studied. It was found that the (MP)_2PT promotes MMA polymerization, and the kinetics of MMA polymerization fits the radical polymerization rate equation. Based on the ESR studies and the end-group analysis the initiation mechanism is proposed.

Visible-light-induced Synthesis of Organic Peroxides via Decarboxylative Couplings of Carboxylic Acids,Alkenes and tert-Butyl Hydroperoxide

Herein,we present a photoinduced,CeCl_(3)-catalyzed three-component decarboxylative reaction that couples carboxylic acids,alkenes and tert-butyl hydroperoxide for the formation of various organic peroxides.The ligand-to-metal charge transfer(LMCT)excitation mode allows the decarboxylative alkylation-peroxidation reaction to occur under mild conditions,and is well applicable to primary,secondary and tertiary carboxylic acids and styrene derivatives.

One stone two birds:electrochemical and colorimetric dual-mode biosensor based on copper peroxide/covalent organic framework nanocomposite for ultrasensentive norovirus detection

Norovirus(NoV)is regarded as one of the most common causes of foodborne diarrhea in the world.It is urgent to identify the pathogenic microorganism of the diarrhea in short time.In this work,we developed an electrochemical and colorimetric dual-mode detection for NoV based on the excellent dual catalytic properties of copper peroxide/COF-NH_(2)nanocomposite(CuO_(2)@COF-NH_(2)).For the colorimetric detection,NoV can be directly detected by the naked eye based on CuO_(2)@COF-NH_(2)as a laccase-like nonazyme using“peptide-NoV-antibody”recognition mode.The colorimetric assay displayed a wide and quality linear detection range from 1 copy/mL to 5000 copies/mL of NoV with a low limit of detection(LOD)of 0.125 copy/mL.For the electrochemical detection of NoV,CuO_(2)@COF-NH_(2)showed an oxidation peak of copper ion from Cu^(+)to Cu^(2+)using“peptide-NoV-antibody”recognition mode.The electrochemical assay showed a linear detection range was 1-5000 copies/mL with a LOD of 0.152 copy/mL.It's worthy to note that this assay does not need other electrical signal molecule,which provide the stable and sensitive electrochemial detection for NoV.The electrochemical and colorimetric dual-mode detection was used to detect NoV in foods and faceal samples,which has the potential for improving food safety and diagnosing of NoV-infected diarrhea.

Organic peroxide production in the CI_2-ethane-air photoreaction system

HPLC along with FT-IR technique was used to study the formation of organic peroxides in the Cl2-ethane-air photoreaction system. Ethyl hydroperoxide (CH3CH21OOH, EHP) and peroxyacetic acid ( CH3C(O)OOH, PAA) were conformed to be the peroxide product in the reaction system. In addition, methyl hydroperoxide (CH3OOH, hydroxymethyl hydroperoxide (HOCH2OOH, HMHP) and two unidentified organic peroxides were detected for the first time. EHP and were the dominant peroxide products. The identification of HMHP showed that Criegee biradical CH2OO may be formed as an intermediate in the oxidation of ethane. Simulation results showed that photooxidation of ethane may make substantial contribution to source of organic peroxides in the atmosphere.

Amperometric Biosensors Sensitive to Organic Peroxides Based on Immobilization of Redox Organic Dyes and Horseradish Peroxidase in Polyester Ionomer Film

Simple and effective organic biosensors sensitive to organic peroxides such as 2 butanone per oxide and tertbutyl hydroperoxide are constructed by immobilizing a series of redox organic dyes and horseradish peroxidase in Eastman AQ polymer film. The organic dyes are methylene blue, methylene green, meldola blue, new methylene blue N and N methyl phenazine methosulphate. The biosensors display high sensitivity and fast response to tertbutyl hydroperoxide and 2 butanone peroxide because of high efficiency of electron transfer between immobilized horseradish peroxidase and the electrode via the redox organic dyes. The comparison of the biosensors employing different organic dyes is made in formal potential, linear range and response time.

Preparation of Polymer-Mineral Nanocomposites Based on Vinyl Monomers and Dispersed Inorganic Oxides

The polymer-mineral composites were synthesized using vinyl monomers styrene, methyl acrylate, and butyl acrylate with nano dispersed oxides Fe2O3, Cr2O3, V2O5 and SiO2 in the presence of benzoyl peroxide and other peroxide initiators. Benzoyl peroxide adsorption on Fe2O3, Cr2O3, and V2O5 surfaces was studied. The adsorption parameters were found: adsorption-desorption equilibrium constants, maximum adsorption, and the area occupied by the molecule benzoyl peroxide on the surface of the adsorbent. The molecular weights of the polymers in the composites and the degree of grafting of the macromolecules of the polymer to the surface of oxides were studied. It has been found that the surface of the dispersed oxides influences the rate of thermal decomposition of the peroxide initiators and the polymerization parameters of the vinyl monomers.