Studies on the mechanism of decomposition of 1-methyl-1-(1-naphthyl)ethyl hydroperoxides to 2-(1-naphthyloxy)propenes

Abstract  

Thermal decomposition of 1-methyl-1-(4-methyl-1-naphthyl)ethyl hydroperoxide under gas chromatography-mass spectroscopy (GC–MS) conditions gives 2-((4-methyl-1-naphthyl)oxy)propene as the main product (50.5%), without any detectable traces of the isomeric 2-((5-methyl-1-naphthyl)oxy)propene. This finding excludes the rearrangement pathway of 1-methyl-1-(1-naphthyl)ethyl hydroperoxides to the corresponding 2-(1-naphthyloxy)propenes, which involves formation of a naphthofuran derivative as an intermediate and transfer of the isopropenyloxy group to the 8 position. This result, as well as our previous density functional theory (DFT) calculations, points to the rearrangement pathway involving an oxirane-type intermediate as the most plausible pathway to 2-(1-naphthyloxy)propenes. This rearrangement is responsible for the unusual inhibition effects of 1-methyl-1-(1-naphthyl)ethyl hydroperoxide on the liquid-phase oxidation of isopropylarenes with oxygen.     

Thermodynamic and transport properties of (1,2-ethanediol + 1-nonanol) at temperatures from (298.15 to 313.15) K

Densities and kinematic viscosities have been measured for (1,2-ethanediol + 1-nonanol) over the temperature range from (298.15 to 313.15) K. The speeds of sound in those mixtures within the temperature range from (293.15 to 313.15) K have been measured as well. Using the measurement results, the molar volumes, isentropic compressibility coefficients, molar isentropic compressibilities, and the corresponding excess and deviation values (excess molar volumes, excess isentropic compressibility coefficients, excess molar isentropic compressibilities, differently defined deviations of the speed of sound, and dynamic viscosity deviations) were calculated. The excess Gibbs free energies estimated by the use of the UNIQUAC model are also reported. The excess molar volumes and Gibbs free energies are positive, whereas the compressibility excesses are s-shaped. The excess and deviation values are expressed by Redlich–Kister polynomials and discussed in terms of variations of the structure of the system caused by the participation of two different alcohol molecules in the dynamic intermolecular association process through hydrogen bonding. The effect of temperature is discussed. The predictive abilities of the McAllister equation for viscosities of the mixtures under test have also been examined.     

Riboflavin as a source of autofluorescence in Eisenia fetida coelomocytes

Immunocompetent cells of earthworms (coelomocytes) contain adherent amoebocytes and large eleocytes (chloragocytes); the latter are filled with numerous granules. We have previously shown that eleocytes of several (but not all) earthworm species exhibit strong autofluorescence detectable by fluorescent microscopy and flow cytometry. In the present article, the molecular origin of eleocytes autofluorescence was elucidated in coelomocytes expelled via dorsal pores in the integument of Eisenia fetida subjected to electric shock (1 min at 4.5 V). Spectrofluorometry (excitation and emission spectra and fluorescence lifetime), together with HPLC analysis of coelomocyte suspensions and supernatants, indicated that riboflavin but not FMN (flavin mononucleotide) or FAD (flavin-adenine dinucleotide) is the main fluorophore responsible for eleocyte fluorescence in this species. Additionally, lipofuscins are suspected to participate in this phenomenon.     

The Effect of Hemp Cake (Cannabis sativa L.) on the Characteristics of Meatballs Stored in Refrigerated Conditions

Hemp cake, a by-product of cold pressing oil from hemp seeds, is a nutritious ingredient that could be used for the production of new or reformulated meat products. The aim of this study was to determine the influence of inclusion of 0.9%, 2.6%, 4.2%, and 7.4% (w/w) hemp cake (Cannabis sativa L.) on the physicochemical and textural properties, oxidation, and sensory acceptance of cooked and vacuum-packed meatballs during refrigerated storage. The addition of 7.4% hemp cake enhanced the amount of dry matter and reduced the content of water. Lightness (L*) and redness (a*) values reduced significantly with higher levels of hemp supplementation. Regardless of the amount of hemp additive, pH, color parameters did not differ significantly during the 12 days of storage. Hemp cake significantly decreased protein and lipid oxidation: the inhibitory effect of adding 7.4% hemp cake on protein carbonyl group formation and TBARS values reached 11.16% and 36.5%, respectively, after 10 days of storage. Sensory analysis revealed that meatballs prepared with 0.9% and 2.6% hemp cake gained higher overall scores. The results indicate that hemp cake, a material considered mainly as waste, may be destined for food purposes and be an alternative ingredient for the production of sustainable meat products.     

Surface Studies on Glass Powders Used in Commercial Glass-Ionomer Dental Cements

The surface properties of three commercial ionomer glass powders, i.e., Fuji IX, Kavitan Plus and Chemadent G-J-W were studied. Samples were analyzed by X-ray fluorescence spectroscopy (XRF), and the density was determined by gas pycnometry. Morphology was studied using scanning electron microscopy (SEM) and laser diffraction (LD) technique, whereas low-temperature nitrogen sorption measurements determined textural parameters like specific surface area and pore volume. Thermal transformations in the materials studied were evaluated by thermogravimetric analysis (TGA), which was carried out in an inert atmosphere between 30 °C and 900 °C. XRF showed that Fuji IX and Kavitan Plus powders were strontium-based, whereas Chemadent G-J-W powder was calcium-based. Powders all had a wide range of particle sizes under SEM and LD measurements. Specific surface areas and pore volumes were in the range 1.42–2.73 m²/g and 0.0029 to 0.0083 cm³/g, respectively, whereas densities were in the range 2.6428–2.8362 g/cm³. Thermogravimetric analysis showed that the glass powders lost mass in a series of steps, with Fuji IX powder showing the highest number, some of which are attributed to the dehydration and decomposition of the polyacrylic acid present in this powder. Mass losses were more straightforward for the other two glasses. All three powders showed distinct losses at around 780 °C and 835 °C, suggesting that similar dehydration steps occur in all these glasses. Other steps, which differed between glass powders, are attributed to variations in states of water-binding on their surfaces.     

Titanium dioxide/graphene oxide composite and its application as an anode material in non-flammable electrolyte based on ionic liquid and sulfolane

A composite of aminosilane-grafted TiO₂ (TA) and graphene oxide (GO) was prepared via a hydrothermal process. The TiO₂/graphene oxide-based (TA/GO) anode was investigated in an ionic liquid electrolyte (0.7 M lithium bis(trifluoromethanesulfonyl)imide (LiNTf₂)) in ionic liquid (N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPyrNTf₂)) at room temperature and in sulfolane (1 M lithium hexafluorophosphate (LiPF₆) in tetramethylene sulfolane (TMS)). Scanning and transmission electron microscopy (SEM and TEM) observations of the anode materials suggested that the electrochemical intercalation/deintercalation process in the ionic liquid electrolyte with vinylene carbonate (VC) leads to small changes on the surface of TA/GO particles. The addition of VC to the electrolyte (0.7 M LiNTf₂ in MPPyrNTf₂ + 10 wt.% VC) considerably increases the anode capacity. Electrodes were tested at different current regimes in the range 5–50 mA g^?1. The capacity of the anode, working at a low current regime of 5 mA g^?1, was ca. 245 mA g^?1, while a current of 50 mA g^?1 resulted in a capacity of 170 mA g^?1. The decrease in anode capacity with increasing current rate was interpreted as the result of kinetic limits of electrode operation. A much lower capacity was observed for the system TA/GO│1 M LiPF₆ in TMS + 10 wt.% VC│Li.     

Chromatography,mass spectrometry,and molecular modeling studies on ammodytoxins

The ammodytoxins (Atxs) are neurotoxic phospholipases which occur in Vipera ammodytes ammodytes (Vaa) snake venom. There are three Atx isoforms, A, B, and C, which differ in only five amino acid positions at the C-terminus but differ substantially in their toxicity. The objective of this study was to establish an analytical method for unambiguous identification of all three isoforms and to use the method to assess a procedure for purification of the most toxic phospholipase, AtxA, from the venom. Isolation procedure for AtxA consisted of isolation of Atx-cross-reactive material (proteins recognized by anti-Atx antibodies), by use of an affinity column, then cation exchange on CIM (Convective Interaction Media) disks. The purification procedure was monitored by means of reversed-phase chromatography (RPC) and mass spectrometry (MS). Although previous cation exchange of the pure isoforms enabled separate elution of AtxA from B and C, separation of AtxA from Atxs mixture was not accomplished. RPC was not able to separate the Atx isoforms, whereas an MS based approach proved to be more powerful. Peptides resulting from tryptic digestion of Atxs which enable differentiation between the three isoforms were successfully detected and their sequences were confirmed by post-source decay (PSD) fragmentation. Separation of Atx isoforms by ion-exchange chromatography is most presumably prevented by Atxs heterodimer formation. The tendency of Atxs to form homodimers and heterodimers of similar stability was confirmed by molecular modeling.     

Raman spectroscopy and imaging: applications in human breast cancer diagnosis

The applications of spectroscopic methods in cancer detection open new possibilities in early stage diagnostics. Raman spectroscopy and Raman imaging represent novel and rapidly developing tools in cancer diagnosis. In the study described in this paper Raman spectroscopy has been employed to examine noncancerous and cancerous human breast tissues of the same patient. The most significant differences between noncancerous and cancerous tissues were found in regions characteristic for the vibrations of carotenoids, lipids and proteins. Particular attention was paid to the role played by unsaturated fatty acids in the differentiation between the noncancerous and the cancerous tissues. Comparison of Raman spectra of the noncancerous and the cancerous tissues with the spectra of oleic, linoleic, α-linolenic, γ-linolenic, docosahexaenoic and eicosapentaenoic acids has been presented. The role of sample preparation in the determination of cancer markers is also discussed in this study.     

Inverse Gas Chromatographic Characterization of Aluminosilicates as Fillers for Abrasive Articles

The surface properties of aluminosilicates (perlites and zeolites)—potential fillers in abrasive articles—have been examined by inverse gas chromatography. The dispersive component of the surface free energy ( $ \gamma_{\text{S}}^{\text{D}} $ ) and K _A and K _D describing the acidity and basicity, respectively, of the fillers were used to express the surface activity of examined materials. The Flory–Huggins parameter, $ \chi_{23}^{'} , $ characterized the interactions between polymer and filler, i.e., interactions between phenolic resin and filler. Zeolites were found to be materials with an active surface layer and relatively high ability to participate in filler–resin interactions. Therefore, they might be considered as potential “replacement material” for standard fillers. The IGC-derived values mentioned above provided useful information about the behavior of fillers during the manufacture and use of abrasive articles.     

Kinetic study of free‐radical polymerization photoinitiated by cyanine‐borate salts. II.

A series of cyanine butyltriphenylborate salts were prepared and tested as initiators of free‐radical polymerization photoinitiated via a photoinduced electron‐transfer process. For the majority of the tested series, the highest rate of photoinitiated free‐radical polymerization was observed when sec‐butyl radicals were formed. Essentially, there was no influence of the quantum yield of the free‐radical formation on the rate of the free‐radical polymerization initiated by the cyanine‐borate salts. The experimental data revealed that the relationship between the rate of polymerization and the free energy change for the electron transfer displayed typical Marcus region kinetic behavior. The photoreduction of the cyanine butyltriphenylborate salts produced colorless products. The efficiency of the bleached‐dye formation had no effect on the overall efficiency of photoinitiated polymerization. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2365–2374, 2000