Metalloporphyrins in Oxidative Catalysis. Oxygen Transfer Reactions of Oxochromium Porphyrins

The oxidation of chloro-5-10,15,20-tetramesitylporphyrinotoiron(III) with peroxyacids affords a reactive oxoiron(IV)-porphyrin cation radical species 2. The characterization of 2 and its oxochromium analogs 3, 4 and 5 are reviewed. The nature of reactive oxochromium species derived from chromyl reagents is also reviewed. The oxidation of triphenylphosphine by CrOTPP (11), CrOTTP (13) and CrOTMP (14) is described. Variations in the rate constants indicate that steric factors affect the rate of oxygen atom transfer. Activation parameters for the oxidation of triphenylphosphine by 14 are ΔH^≠ = 6.96 kcal/mol and ΔS^≠ = −39 eu. The oxidation of t-butylphenylcarbinol (18) by CrOTPP gave predominantly benzaldehyde via carbon—carbon bond cleavage while the chromium(III) porphyrin-catalyzed oxidation of 18 by iodosylbenzene afforded t-butylphenylketone.     

Acrylonitrile-based copolymers: Synthesis,characterization, and formation of ultrafiltration membranes utilized for the immobilization of proteins

Various high molecular weight copolymers of acrylonitrile and a vinyl comonomer containing an aryl amine, a pyridine, or an aliphatic hydroxyl group were synthesized via slurry polymerization techniques so as to contain from 1 to 15 mol % functional comonomer. The comonomer content was quantitated by ultraviolet absorbance, base titration of acid polymer salts, and/or relative chemical reactivity with trichloro-s-triazine. Thin films were cast from copolymer solutions, coagulated into unsupported ultrafiltration membrances, and characterized with respect to both water permeability and pore size distribution. Analysis by size exclusion chromatography of the membrane permeate of a pool of dextran fractions yielded a continuous distribution curve for membrane pore size over the range 1.5 to 70 nm. The ultrafiltration membranes were used for protein immobilization after appropriate chemical activation. The three distinct types of functional copolymers gave comparable results for α-chymotrypsin, with protein weight loadings of 6–12% and 40–65% retention of enzymatic specific activity.     

Low backmixing in multistage agitated contactors used as reactors

The objective of the study was to test the validity of an available backmix correlation in the low backmix regime required by multistage agitated contactors used as reactors. The correlation was found to be inapplicable, and new equation forms were developed to fit the new experimental data. Keys to low backmix rates are a small annular area around the shaft compared to the column cross-sectional area and an extended annular path length.     

Experimental Study of Porous Gel Sintering

Formation and disappearance of closed pores in silica gel during sintering were experimentally detected using a light-scattering technique. The disappearance of closed pores is strongly influenced by the atmosphere in which the gel is sintered.     

A test for the statistical significance of DNA sequence similarities for application in databank searches

A method is developed, based on word-searching, which provides a rapid test for the statistical significance of DNA sequence similarities for use in databank searching. The method makes allowance for the lengths and dinucleotide compositions of the sequences being compared. A way is also described to calculate the power of the test, i.e. the probability of detecting a given similarity as being statistically significant. The effects on the power of the test of the scoring method, word length, sequence length, and sequence composition are examined. A novel scoring method is shown to be superior to the method currently used in most word-searching algorithms.     

Biochemical oxidation of caprolactam-containing wastewater from the production of synthetic fibres

Conclusions The chemical mutagenesis method is recommended for use in local purification installations for cleaning up of caprolactam-containing wastewater.Use of this method permits one to carry out a biochemical clean-up of wastewater having a caprolactam content up to 600 mg/liter while increasing the oxidative power of the aeration tank by a factor of two.Translated from Khimicheskie Volokna, No. 6, p. 46, November–December, 1985.     

Numerical solution for shape optimization of an impactor penetrating into a semi-infinite target

The shape of the impactor with the maximum depth of penetration (DOP) for a given impact velocity is found using a numerical procedure for solving a corresponding non-classical variational problem. It is shown that the optimum shape in a general case is close to a blunt cone. The variation of the optimal shape of the impactor and the dependence of the DOP vs. the initial (impact) velocity and friction coefficient is studied. The analysis is performed also for optimal conical impactors.     

Pool boiling on a superhydrophilic surface

Titanium Dioxide, TiO₂, is a photocatalyst with a unique characteristic. A surface coated with TiO₂ exhibits an extremely high affinity for water when exposed to UV light and the contact angle decreases nearly to zero. Inversely, the contact angle increases when the surface is shielded from UV. This superhydrophilic nature gives a self-cleaning effect to the coated surface and has already been applied to some construction materials, car coatings and so on. We applied this property to the enhancement of boiling heat transfer. An experiment involving the pool boiling of pure water has been performed to make clear the effect of high wettability on heat transfer characteristics. The heat transfer surface is a vertical copper cylinder of 17 mm in diameter and the measurement has been done at saturated temperature and in a steady state. Both TiO₂-coated and non-coated surfaces were used for comparison. In the case of the TiO₂-coated surface, it is exposed to UV light for a few hours before experiment and it is found that the maximum heat flux (CHF) is about two times larger than that of the uncoated surface. The temperature at minimum heat flux (MHF) for the superhydrophilic surface is higher by 100 K than that for the normal one. The superhydrophilic surface can be an ideal heat transfer surface. Copyright © 2002 John Wiley & Sons, Ltd.     

Erosion und Korrosion of metallischer Werkstoffe in feststoffhaltigen Wässern

Erosion and corrosion of metallic materials in particle containing aqueous solutions The combined effect and mutual influence, respectively, of erosion and corrosion of metallic materials in particle containing flows was investigated. Materials under investigation are carbon steel of different hardness levels, ferritic chromium steel, austenitic stainless steel and brass. Corrosive medium was deionized water, acid (pH 4.5), alkaline (pH 10) and chloride (3% NaCl) solution. Quartz particles were used as abrasive at various particle concentrations, grain sizes and flow velocities. For comparison, tests were performed with pure water and under conditions of idle corrosion. Mechanical or corrosive influences dominate depending on material and test conditions, in some cases, synergistic effects of both mechanisms cause an increased mass loss.