A novel and efficient synthesis of porphine

meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.     

A note on the unsteady boundary layers over a flat plate

The unsteady boundary layer over a semi-infinite flat plate was investigated in this paper. The flow involves the unsteady flow over a flat plate with leading edge accretion or ablation. The momentum boundary layer was further analyzed and it was shown that the leading edge ablation had a similar effect to the wall mass injection or upstream wall movement making the fluid blown away from the wall. The thermal boundary layer of the same flow was also studied. Results show that the leading edge accretion or ablation can greatly change the fluid motion and the heat transfer characteristics.     

Effects of aldehyde or dipyrromethane substituents on the reaction course leading to meso-substituted porphyrins

To better understand the effects of diverse substituents on reactions leading to porphyrins, pyrrole+aldehyde condensations and related reactions of dipyrromethanes were examined. The course of pyrrole+aldehyde condensations was investigated by monitoring the yield of porphyrin (by UV-Vis spectroscopy), reaction of aldehyde (by TLC), and changes in the composition of oligomers (by laser desorption mass spectrometry). Reaction reversibility was examined via exchange experiments. Reversibility of reactions leading to porphyrin was further probed with studies of dipyrromethanes. The reaction course was found to depend on the nature of the substituent and the acid catalyst. Alkyl or electron-donating substituents displayed levels of reversibility (exchange/scrambling) on par or greater than that of the phenyl substituent, whereas electron-withdrawing or sterically bulky substituents exhibited little to no reversibility. The results obtained provide insight into the electronic and steric effects of different substituents and should facilitate the design of synthetic plans for preparing porphyrinic macrocycles.     

Modeling of radiative heat transfer in an axisymmetric cylindrical enclosure with participating medium

Radiative heat transfer in an axisymmetric enclosure with absorbing, emitting, and scattering medium is studied here by using the different methods such as MDOM, FVM, and MFVM with emphasis on the treatment of angular derivative term, which appears in curvilinear coordinates due to angular redistribution. After final discretization equation for MFVM is introduced by using the step scheme and directional weights, the present approach is validated by applying it to three different benchmarking problems with absorbing, emitting, and scattering medium. All of the results presented here support its accuracy as well as moderate efficiency. Finally, the present approaches are applied to a truncated cone-shaped enclosure as a body-fitted geometry case.     

Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

Electron-stimulated desorption of D (H) from condensed D2O (H2O) films

The electron-stimulated desorption (ESD) of D⁻ and H⁻ ions from condensed D₂O and H₂O films is investigated. Three low-energy peaks are observed in the ESD anion yield, which are identified as arising from excitation of ²B₁, ²A₁ and ²B₂ dissociative electron attachment (DEA) resonances. Additional structure is observed between 18 and 32 eV, which may be due to ion pair formation or to DEA resonances involving the 2a₁ orbital. The ion yield resulting from excitation of the ²B₁ resonance increases as the film is heated. We attribute the increase in the ion yield to thermally induced hydrogen bond breaking near the surface, which enhances the lifetimes of the excited states that lead to desorption.     

Annealing and measurement temperature dependence of W2B5-based rectifying contacts to n-GaN

The thermal stability and measurement temperature dependence of Schottky contact characteristics on n-GaN using a W₂B₅/Ti/Au metallization scheme was studied using current-voltage (I-V), scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) measurements. The elemental profile obtained from samples annealed at 350 °C showed some titanium diffusion into the gold layer but little other difference from the as-deposited wafer. Annealing at 700 °C produced significant diffusion of titanium. The Schottky barrier height increased with anneal temperature up to 200 °C, reaching a maximum value of 0.65 eV, but decreased at higher annealing temperatures. The reverse breakdown voltage from diodes fabricated using the W₂B₅-based contacts showed a similar dependence. The reverse current magnitude was larger than predicted by thermionic emission alone. The barrier height showed only minor changes with measurement temperature up to 150 °C.     

<Emphasis Type="Italic">Comment on</Emphasis>¶Low temperature specific heat of blue bronze K <Emphasis Type="Bold">0.30</Emphasis>MoO <Emphasis Type="Bold">3</Emphasis>, by J. Odin,J.C. Lasjaunias,K. Biljaković, K. Hasselbach,and P. Monceau

Eur. Phys. J. B 24, 315 (2001) Here we comment on a recently published paper on the presence of a phason contribution in the low temperature heat capacity data of the charge-density-wave compounds K_0.3MoO₃ and (TaSe₄)₂I. We have shown that the anomaly in the C _P / T ³ data reported by Odin et al. is straightforwardly interpreted in terms of low energy phonon modes resulting from the peculiar topology of these compounds. Received 21 February 2002 Published online 19 July 2002     

Adhesion studies of latex film surfaces on the meso- and nanoscale

In this paper the effects of surface roughness and annealing temperature (T) of latex coating films on adhesion are discussed for the different stages of the film formation process. The surface free energy of latex films was assessed in terms of practical work of adhesion (W) (or adherence) using a custom-built adhesion-testing device (ATD), atomic force microscopy (AFM), and contact angle measurements. For preannealed latex films surface roughness averages (R_a) were determined from AFM height images and were related to the values of W obtained from ATD measurements at room temperature. The results obtained using these tests exhibiting surface behavior on different length scales indicate a dependence of the measured adhesion on surface roughness and temperature, as well as on the length scale of the measurements.First preannealed samples were studied, which were obtained by heat treatment above the respective glass transition temperatures (T_g). Increasing the temperature of preannealing resulted in a decrease of the adherence observed in ATD experiments at room temperature. However, on the nanoscale, using AFM, no significant variation of the adherence was observed. This observation can be explained by roughness arguments. Preannealing decreases roughness which results in lower adherence values measured by ATD while for essentially single asperity AFM experiments roughness has an insignificant effect. Specimens were also annealed over a constant period of time (90 min) at different temperatures. At the end of the heat treatment, adhesion was measured at the treatment temperature by ATD. The amplified effect of temperature observed in this case on adherence is attributed to the combination of roughness decrease and increasing test temperature. In a third set of experiments completely annealed samples were studied by ATD as well as by AFM as a function of temperature. With increasing T values ATD showed a decrease in adherence, which is attributed to a decreasing surface free energy of the annealed films at elevated T values. AFM, on the other hand, showed an opposite trend which is assigned to increasing penetration of the tip into the tip/wetting polymer samples versus increasing temperature. Finally, annealing isotherms as a function of time were investigated by ATD in situ at different temperatures. This last set of experiments allowed us to optimize annealing time and temperature to achieve complete curing.