THE SECONDARY REACTION IN THE CONDENSATION OF 1-METHYL-2-METHYLTHIO-IMIDAZOLINE WITH ACTIVE METHYLENE COMPOUNDS

Mono-substituted heterocyclic ketene aminals are formed by the reaction of 1-methyl-2-methylthio-imidazoline with active methylene compounds containinq an acetyl or benzoyl group by the elimination of both a methylthio and an acyl group.This is resulted by the secondary reactio of the produced methanethiol to attack the more active carbonyl group.

Modeling and Simulation of the Autocatalytic Kinetics of Haemoglobin SS Polymerization: Onset of Polymerization

We report a fresh and simpler approach to the modelling of the kinetics of the polymerization of Hb SS in sickle cell patients that couples the kinetics and the hydrodynamics of blood flow in mechanistic understanding of the process. The well-known two-step autocatalytic reaction scheme was used for the polymerization reaction with the assumption of simpler first-order reaction scheme for each stage. In addition, the forces acting on a particle in motion were also introduced to account for compelling settling of the red cells that lead to vessel occlusion (vaso-occlusion). A first attempt on the prediction of vessel blockage was made using this novel model. The time for the onset of the polymerization reaction was derived from hydrodynamic considerations and kinetics while the kinetic rate constants were obtained from the autocatalytic nature of the reaction. Experimental data for model validation were obtained from recruited SS patients and in vitro data of Hofrichter. Over 100 volunteers were recruited for participation in this work but less than 40% met the inclusion criteria. Participants were of age range 13 - 43 (with a mean of 26 ± 8 years) for SCD patients and 18 - 43 (with a mean of 28 ± 7 years) for control participants. Blood indices and Transcranial Doppler (TCD) test parameters of all participants were the principal parameters used for model validation. Constant k2/k1 ratios was obtained for individual in vivo/in vitro system. This ratio is unique for any individual, independent on protein sequence and also suggests the degree of expression of the symptoms of Sickle Cell Disease (SCD) with higher values reflecting greater propensity to pain crisis. Delay time, tD, was found to have an inverse relationship with the kinetic constant for the residual reaction, k1. Therefore, long delay times calculated, offer insight on why SCD patients are not in perpetual crises because enough time is provided the cells to escape microcirculation while keeping the residual reaction at the minimum. Sensitivity analysis was carried out to obviate the limitations encountered in the course of the work. Results showed the onset of occlusion to be most sensitive to the diameter of the blood vessel.

Effect of secondary MO interaction on the regiospecificity in the reactions of α-ionones with singlet oxygen

The eme reactions of α-ionones with singlet oxygen were examined to ascertain the effect of secondary Me interaction between the reactants on the reaction regiospecificity. Exclusive formation of 3-hydroxy-γ-ionones found in the reactions reveals favorable interaction of singlet oxygen with the acyclic α-hydrogen atom,On the other hand,no formation of 3-hy- droxy-β-ionones implies that the steric requirement was not met for the bond formation between zwitterionic perepoxide with C_1-hydrogen in the process.The MMP21 and MNDO calculations indicate minus value of the secondary interaction energy for the aeyelie α-hydrogen abstrac- tion and a repulsion between the oxygen with C_1-hydrogen atom.Twisting tilting of the double bond may account for favorable attack of singlet oxygen on C_3.An explanation of the excellent regiospecificity was addressed and placed in proper mechanic prospective.

Analysis of the linkage positions and isomers of monosaccharide units in oligosaccharides by negative secondary ion mass spectrometry in combination with the stereoselective reaction with substituted boronic acid

The negative secondary ion mass spectrometry,in combination with the stereoselective derivatizations with substituted boronic acid RB(OH)_2,was used in the analysis of fourteen oligosac- charides.The mass spectra of the derivatives provide information on their linkage Positions and iso- merism of the individual monoscaccharide units.The results indicated that among the derivatives of the oligosaccharides analyzed,those with 1—4 and 1—6 linkages all presented the ion peaks at m/z 287,sometimes one more peak at m/z 449.Furthermore,a relationship was found between the linkage positions and the intensity orders of the derivative ions.Finally,the derivatives of the disaccharides with a galactose presented an intense ion peak at m/z 347,and those of oligosaccharides with 1—6 linkage to a galactose at terminal presented the ion at m/z 317.In the case of oligosaccharides with a fructose residue,characteristic ion of m/z 155 was produced.The conditions of stereoselective derivatizations and mass spectrometry were studied,in order to obtain a better reproducibility of the mass spectra.

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol （SOA） formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer （SMPS） during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer （VUV-ATOFMS）. Gas chromatograph/mass spectrometer （GC/MS） analyses of oxidation products of anthracene were carried out for assigning the time-of-flight （TOF） mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.

Pyrolysis characteristics of waste tire particles in fixed-bed reactor with internals

This study investigated the characteristics of pyrolysis for waste tire particles in the newly developed fixed-bed reactor with internals that are a central gas collection channel mounted inside reactor.And a few metallic plates vertically welded on the internal wall of the reactors and extending to the region closing their central gas collection pipe walls.Experiments were conducted in two laboratory fixed bed reactors with or without the internals.The results shown that employing internals produced more light oil at externally heating temperatures above 700℃due to the inhibited secondary reactions in the reactor.The oil from the reactor with internals contained more aliphatic hydrocarbons and fewer aromatic hydrocarbons,leading to its higher H/C atomic ratios as for crude petroleum oil.The char yield was relatively stable for two beds and showed the higher heating values(HHVs)of about 23 MJ/kg.The gaseous product of pyrolysis mainly consisted of H2 and CH4,but the use of internals led to less pyrolysis gas through its promotion of oil production.