Ultrasound-Assisted Green Synthesis of Dialkyl Peroxides under Phase-Transfer Catalysis Conditions.

The dialkyl peroxides, which contain a thermally unstable oxygen-oxygen bond, are an important source of radical initiators and cross-linking agents. New efficient and green methods for their synthesis are still being sought. Herein, ultrasound-assisted synthesis of dialkyl peroxides from alkyl hydroperoxides and alkyl bromides in the presence of an aqueous solution of an inorganic base was systematically studied under phase-transfer catalysis (PTC) conditions. The process run in a tri-liquid system in which polyethylene glycol as a phase-transfer catalyst formed a third liquid phase between the organic and inorganic phases. The use of ultrasound provided high yields of organic peroxides (70-99%) in significantly shorter reaction times (1.5 h) in comparison to reaction with magnetic stirring (5.0 h). In turn, conducting the reaction in the tri-liquid PTC system allowed easy separation of the catalyst and its multiple use without significant loss of activity.

Carbon nanofiber-based luminol-biotin probe for sensitive chemiluminescence detection of protein.

A carbon nanofiber-based luminol-biotin probe was synthesized for the sensitive chemiluminescence (CL) detection of a target protein by grafting luminol and biotin onto an oxidized carbon nanofiber. This carbon nanofiber was prepared by chemical vapor-deposition with methane in the presence of the Ni-Cu-MgO catalyst, which was followed by oxidization with HNO3-H2SO4 to produce a carboxyl group on the surface of the nanofiber. The material was grafted with luminol and biotin by means of a standard carbodiimide activation of COOH groups to produce corresponding amides. The substance was water-soluble and thus could be utilized as a sensitive CL probe for a protein assay. The probe showed highly specific affinity towards the biotin-labeled antibody via a streptavidin-biotin interaction. The detection limit for this model assay was approximately 0.2 pmol of the biotinized IgG spotted on a polyvinylidene fluoride (PVDF) membrane. Nonspecific binding to other proteins was not observed. Therefore, the synthesized carbon nanofiber-based CL probe may be useful for a sensitive and specific analysis of the target protein.

Application of response surface methodology (RSM) to the optimization of a post-column luminol chemiluminescence analysis of silyl peroxides.

The possibility of the utilization of chemiluminescence post-column luminol oxidation (CL) in a HPLC system for silyl peroxides analysis has been investigated. The conditions of HPLC separation for 12 silyl peroxides, representing bissilyl and alkyl-silyl peroxides, as well as their potential impurities, were established. Optimal chemiluminescent post-column reaction conditions were found using central composite design (CCD) and response surface methodology (RSM). The interaction effects of four of the most important operating variables - the concentrations of luminol, hemin, sodium hydroxide and the post-column solution flow rate - on the light intensity were evaluated. The optimized conditions for analysis were the same for bissilyl and alkyl-silyl peroxides for the base concentration (0.03 M), the luminol concentration (0.4 g L(-1)) and the hemin concentration (0.3 g L(-1)). The only differences occurred in a reagent flow rate (for bissilyl peroxide -0.3 mL min(-1) and for alkyl-silyl peroxides -0.9 mL min(-1)). Under optimal conditions, the detection limits were in the 0.07-0.16 nM range for bissilyl, and 0.53-1.01 for alkyl-silyl peroxides. The calibration curves were linear in the 0.25-3 nM range for bissilyl and the 2.5-25 range for alkyl-silyl peroxides. Intra-day and inter-day precision was lower than 5.5% for each tested concentration level. A mechanism of luminol oxidation by silyl peroxides involving a hydrolysis step with the formation of hydrogen peroxide or hydroperoxide was proposed.

The influence of dioxygen on luminol chemiluminescence.

Assays of peroxy compounds are commonly performed after chromatographic separation of analysed mixtures. In high-performance liquid chromatography (HPLC), solvent reservoirs are sparged by helium or inline vacuum-degassed in order to control the compressibility of the solvents for efficient pumping. In this study, we investigated the influence of degassing the reaction solution on the light output of the hemin-catalyzed luminol oxidation by various oxidants. We found that, when t-butyl hydroperoxide, hydrogen peroxide, n-butyl hydroperoxide, iodosobenzene and iodobenzene diacetate were used as oxidants, the luminol chemiluminescence was lowered by 50-70% compared with an equilibrated and degassed solution. The opposite effect was observed when dibenzoyl peroxide and 3-chloroperoxybenzoic acid were used as oxidants, as the chemiluminescence increased by approximately 20-30%. The reduced chemiluminescence was explained based on the known role of dioxygen in luminol chemiluminescence. The enhancement of chemiluminescence was rationalized by suggesting an alternative mechanism of luminol oxidation valid for peroxyacids and diacyl peroxides in which the reaction of a peroxyacid anion with the diazaquinone led to light emission with a higher quantum yield than the usual path, which is suppressed by the removal of dioxygen from the reaction solution.

Chemiluminescence detection of organic peroxides in a two-phase system.

Potential application of chemiluminescence (CL) reaction of luminol for detection of organic peroxides by HPLC post-column reaction using an immiscible apolar eluent (hexane) with aqueous solution of luminol has been proposed. The positive influence of the addition of an anionic surface-active agent--sodium dodecyl sulphate (SDS) to the luminol solution on the CL intensity has been observed. The sensitivity of the method is greater for peroxyacid and hydroperoxide tested, and lesser for diacyl peroxide as compared to system with polar eluent miscible with solution of luminol. Our interpretation of observed results based on the extraction efficiency, CL kinetics and microemulsion formation has been suggested.

Screening for pyrrolizidine alkaloids in plant materials by electron ionization RP-HPLC-MS with thermabeam interface.

Plant samples from leaves of Cerinthe minor, Cynoglossum clandestinum, Echium tuberculatum (as well roots), Eritrichium rupestre, Lithospermum purpureo-coerulem, Nonnea lutea, Nonnea setosa, Onosma stellulatum and Cynoglossum amabile were screened for toxic pyrrolizidine alkaloids (PAs) with a newly elaborated procedure comprising gradient HPLC with diode array (DAD) and thermabeam electron impact mass spectrometry (EI-MS). Dried plant material was extracted with boiling 1% tartaric acid in methanol for 2 h on an electric basket and crude extracts purified with cation-exchange solid phase extraction (CE-SPE). Purified extracts containing alkaloids were separated on Zorbax SB RP18 stationary phase in gradient of 0.1% formic acid in methanol. The flow rate was 0.25 mL/min and was suitable both for DAD and EI MS detections. Applied gradient procedure permitted quite sufficient separation of PAs in various plant extracts. On the basis of EI MS spectra, toxic PAs with unsaturated 1,2-double bond in the necine moiety were found in all plant materials and in nine of them (excluding only Cynoglossum amabile) for the fi rst time. They included the following types of structures: 9- and 7-viridifloryl-retronecine monoesters, 9-angeloyl-7-viridifloryl-retronecine, 9-angeloyl-retronecine diester, 9-viridifloryl-retronecine saturated ester, 7-angeloyl-9-viridifloryl-retronecine, 7-angeloyl-9-echimidinyl-retronecine, trachelanthamine and others. Selected ion monitoring (SIM) chromatograms at m/z 119, 120 and 136 together with analysis of UV spectra from DAD detector can be applied in rapid screening for toxic PAs in new plant extracts but to obtain detailed structural information (molecular weight and stereochemistry) more expensive hyphenation is required. Consumption of all analysed plants should be avoided as carcinogenic and hepatotoxic properties of the alkaloids detected are expected.

Application of chemiluminescence for the detection of peroxy compounds in high-performance liquid chromatography.

The possibility of applying post-column reaction and chemiluminescence to determine organic peroxy compounds by RP-HPLC was investigated. Conditions of qualitative and quantitative analyses have been established. The applicability of the method has been demonstrated for a series of compounds representative of the most important groups of peroxy-type compounds, that is, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxyacids.