Correlation of Plasma Sprayed Coating Deposition Efficiency with Volume Flux Measurements by Phase Doppler Anemometry (PDA)

The use of phase-Doppler anemometry (PDA) to characterize the detail in-flight plasma sprayed particle behavior has been demonstrated previously [Ma et al. Plasma Chem Plasma Process 24(1):85; 25(1):56] The present articles shows further that a direct relationship may exist between the PDA measured particle volume flux and the coating microstructure and deposition efficiency (DE). In the situation when the precise particle temperature information is not available, the PDA measured particle volume flux may provide an alternative to predict quantitatively the variation of the coating microstructure and the DE. By monitoring the in-flight particle volume flux variations, instead of the particle velocity, size and temperature individually and simultaneously, the optimal settings of the plasma spraying parameters may also be determined conveniently. However, it is noted that the effective applications of such approach depend largely on the particle surface morphology and the pre-determination of the particle size range.     

Nickel peroxide: A more probable intermediate in the Ni(II)‐catalyzed decomposition of peroxomonosulfate

The Ni(II) ion catalyzed thermal decomposition of peroxomonosulfate (PMS) was studied in the pH range 3.42–5.89. The rate is first order in [PMS] and Ni(II) ion concentrations. At pH greater than or equal to 5.23, the reaction becomes zero order in [PMS] and this changeover in the order of the reaction occurs at a higher concentration of nickel ions. The first‐order kinetics in PMS can be explained as a rate‐limiting step and is the transformation of nickel peroxomonosulfate into nickel peroxide. This peroxide intermediate reacts rapidly with another PMS to give oxygen and Ni(II). The formation of nickel peroxide is associated with a small negative or nearly zero entropy of activation. The zero‐order kinetics in [PMS] can be explained by the fact that the hydrolysis of aquated nickel(II) ions into hydroxocompounds is the rate‐limiting step. The turnover number is 2 at pH 3.42 and increases with pH. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 320–237, 2007     

A convergent approach to the formal total synthesis of hemibrevetoxin B

A convergent synthesis of the key synthetic intermediate of hemibrevetoxin B was achieved via the intramolecular allylation of an α-chloroacetoxy ether and subsequent ring-closing metathesis.     

Inner-sphere oxidation of iron(II) by tris(malonato)cobaltate(III)

The kinetics of oxidation of Fe²⁺ by [Co(C₃H₂O₄)₃]^3? in acidic solutions at 605 nm showed a simple first-order dependence in each reactant concentration. The second-order rate constant dependence on [H⁺] is in accordance with eqn (i) k₂ = k′₂ + k₃[H⁺] (i) where k′₂ and k₃ have values of 73.4 ± 14.0 M ^?1 s^?1 and 353 ± 41 M^?2 s^?1, respectively, at 1.0 M ionic strength (NaClO₄) and 25°C. At 310 nm the formation and decomposition of an intermediate, believed to be [FeC₃H₂O₄]⁺, was observed. The increase in the rate of oxidation with increasing [H⁺] was interpreted in terms of a “one-ended” dissociation mechanism which facilitates chelation of Fe₂₊ by the carbonyl oxygens of malonate in the transition state.     

Synthesis and biological activities of analogs of a lipid A biosynthetic precursor: 1-O-phosphonooxyethyl-4'-O-phosphono-disaccharides with (R)-3-hydroxytetradecanoyl or tetradecanoyl groups at positions 2, 3, 2' and 3'.

Two novel analogs of a biosynthetic precursor of lipid A (2) were synthesized. The one analog (3) has acyl groups identical to those of 2, and the other (4) has tetradecanoyl groups in place of the (R)-3-hydroxytetradecanoyl groups of 2. Both 3 and 4 possess an alpha-glycosidically-bound phosphonooxyethyl group in place of the alpha-glycosyl phosphate group of 2. Compounds 3 and 4 exhibited definite antitumor activity against Meth A fibrosarcoma and low toxicity in rabbits, as the original compound 2 does. The replacement of the hydroxytetradecanoyl groups with tetradecanoyl groups barely affected the antitumor activity, but slightly enhanced the toxicity in rabbits.     

Synthesis of pyrido[1,2-c][1,3]benzoxazines based on 1-benzyl-3-hydroxy-3-methyl-6-(2-benzyloxyphenyl)-4-piperidones

The stereomeric 1-benzyl-3-hydroxy-3-methyl-6e-(2-bemyloxyphenyl)-4-piperidones on debenzylation and subsequent reaction with formaldehyde are converted into cis- and trans-1,3,4-10b-tetrahydro-3-hydroxy-3-methyl-2-oxopyrido-[1,2-c][1,3]benzoxazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 124–127, January, 1991.     

GeneralizedG-theory

A generalization of theG-theory defined by A. Heilet al. is presented.