Study of the spontaneous formation of organic layers on carbon and metal surfaces from diazonium salts

This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur.     

The dehydration of copper(II) acetate monohydrate

The thermal dehydration of copper(II) acetate hydrate has been studied between 353 and 406 K, over a range of humidities. The dehydration is controlled by nucleation-and-growth kinetics at low temperatures, with an activation energy of 154 kJ·mol⁻¹, which changes to contracting-disc kinetics at higher temperatures with a lower activation energy of 76 kJ·mol⁻¹. Frequency factors have also been derived; the value for the high temperature process is low (10⁷s⁻¹) and that for the low temperature step is high (10¹⁷s⁻¹). Optical microscopy has been used to clarify the bulk kinetics; there is evidence for a reactive layer at the surface of the decomposing solid. In celebration of the 60^th birthday of Dr Andrew K. Galwey     

Thermal decomposition of hexamminecobalt(III) chloride

The results of comparative thermal analysis (TG-DTG-DTA-DSC) of the thermal decomposition of hexamminecobalt(III) chloride in air atmosphere are reported. The kinetics and mechanism of the thermal decomposition, the process enthalpy and the variation in specific thermal capacity of the solid product reaction with temperature were determined.     

A thermoanalytical study of the formation and activation of novel copper-carbon catalysts

Simultaneous DSC-TG and DTA-TG were used to investigate the calatytic effect of the metal on the thermal decomposition of a cellulose matrix containing small copper particles. The techniques were also used to demonstrate the effect of the metal particles on the subsequent activation of the carbon matrix, a process which develops the pore structure necessary to expose the metal particles to the gas phase. Temperature programmed desorption was used to study the initial mass loss found on activation. To quantify the catalytic effect of the copper particles on the activation process an estimate was made of the activation energy of the catalysed and uncatalysed reactions. The work gives valuable information on the processes involved in the preparation of a new range of metal-carbon catalysts. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C±0·l°C. The system follows non-ideal radical kinetics (R _p ∝ [M]^1·4 [I]^0·44 @#@) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value ofk ₂ ^p /k _t were 64 kJmol⁻¹ and 0.173 × 10⁻³ 1 mol⁻¹ s⁻¹ respectively     

Reactivity of a Ti–45.9Al–8Nb alloy in air at 700–900°C

A Ti–45.9Al–8Nb (at%) alloy with a lamellar structure (γ+α₂) was oxidised in air at 700, 800, 850 and 900°C in isothermal and thermal cycling conditions. The reaction progress was followed by thermogravimetric measurements. In isothermal conditions the oxidation kinetics followed approximately a parabolic rate law and the rate constants ranged from about 10^–12 kg² m^–4 s^–1 at 700°C to 10^–10 kg² m^–4 s^–1 at 900°C. The oxide scales were built of Al₂O₃ and TiO₂, the former being the main component of the outermost layer. The oxidation behaviour of Ti–45.9Al–8Nb was referred to a commercial titanium alloy, WT4 (Ti–6Al–1Mn), and selected oxidation-resistant alloys.     

Kinetics and mechanism of free-surface vaporization of zinc, cadmium and mercury oxides analyzed by the third-law method

On the basis of critical comparison of experimental and theoretical values of the E parameter and investigation of the retardation effect of oxygen on the evaporation rate of ZnO, CdO and HgO, it was concluded that the dissociative evaporation of ZnO and HgO proceeds with releasing of atomic oxygen (O) as a primary product of decomposition. By contrast, the mechanism of dissociative evaporation of CdO corresponds to the equilibrium reaction with releasing of molecular oxygen (O₂) as a primary product of decomposition. As was shown, this difference in mechanisms is not related with interatomic OO distances in these oxides. From the analysis of crystal structure for 12 different oxides, which evaporate with releasing of atomic oxygen, and for 13 compounds, which evaporate with releasing of molecular oxygen, it was revealed that the first mechanism is observed for all oxides with the cubic crystal structure. It was proposed that a decisive role in this difference belongs to a local symmetry in the position of O atoms.     

Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase

Stimuli‐responsive poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes were synthesized by (1) the radical copolymerization of N‐isopropylacrylamide and maleic anhydride with α,α′‐azobisisobutyronitrile as an initiator in 1,4‐dioxane at 65 °C under a nitrogen atmosphere, (2) the polyesterification (grafting) of prepared poly(N‐isopropylacrylamide‐co‐maleic anhydride) containing less than 20 mol % anhydride units with α‐hydroxy‐ω‐methoxy‐poly(ethylene oxide)s having different number‐average molecular weights (M_n = 4000, 10,000, or 20,000), and (3) the incorporation of macrobranched copolymers with poly(ethylene imine) (M_n = 60,000). The composition and structure of the synthesized copolymer systems were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy, and chemical and elemental analyses. The important properties of the copolymer systems (e.g., the viscosity, thermal and pH sensitivities, and lower critical solution temperature behavior) changed with increases in the molecular weight, composition, and length of the macrobranched hydrophobic domains. These copolymers with reactive anhydride and carboxylic groups were used for the stabilization of penicillin G acylase (PGA). The conjugation of the enzyme with the copolymers significantly increased the thermal stability of PGA (three times at 45 °C and two times at 65 °C). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1580–1593, 2003