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.     

Self-monitoring processes and Holland Vocational Preferences among college students.

Examined the association between self-monitoring and occupational preferences. 237 undergraduates completed Snyder and Gangestad's (1986) revised self-monitoring scale and Holland's (1977) Vocational Preference Inventory (VPI). Regression analyses showed that men who valued congruence between their beliefs and behavior (i.e., low self-monitors) preferred social occupations. Men who were inclined to modify their behavior to fit social situations (i.e., high self-monitors) preferred enterprising occupations. In contrast, high self-monitoring women preferred artistic occupations. It is argued that these gender-neutral occupations permit high self-monitoring women to use their social skills but without the constraints found in male dominated enterprising occupations. Results support the assumption that people prefer occupations compatible with their social skills. Implications for career counseling and further research are noted. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

How social comparison mediates the relation between ability-grouping practices and students' achievement expectancies in mathematics.

This investigation tested the hypothesis that social comparison processes mediate the relation between ability-grouping practices in mathematics and students' achievement expectancies in a district-wide sample of 6th graders (N?=?452). Compared with between-classroom ability grouping, within-classroom grouping raises high achievers' achievement expectancies, math grades, and tendency to make downward comparisons (i.e., with a classmate who is worse at math). Within-classroom grouping lowers low achievers' expectancies and math grades and increases their tendency to make upward comparisons. When controls for the direction of students' social comparison choices and for their mathematics grades are introduced, the independent effect of ability grouping on achievement expectancies is consistently and substantially reduced. It is argued that ability-grouping practices constrain the choices available to students and teachers for social comparison of abilities and thereby influence the frame of reference students use for self-assessment and teachers use for assigning grades. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Ethical issues concerning expert systems' applications in education

This article traces the connection between expert systems used as consultants in medicine and their design for instructional purposes in education. It is suggested that there are important differences between these applications. Recognizing these differences leads to the view that the development of intelligent computer-assisted instructions (ICAI) should be guided by empirical research into social/psychological consequences and by ethical inquiries into the acceptability of those consequences. Three proposals are put forward: (1) that the pedagogical role of intelligent CAI be clarified, (2) that forms of intelligent CAI be developed that aim primarily at refining rather than replacing human judgements, and (3) that ICAI research and development projects contain components which address ethical and social/psychological components and which are equitably-funded, integral parts of the overall development effort.This work was supported in part by funds from the Foundation of the University of North Carolina at Charlotte and from the State of North Carolina. An earlier version of this paper was read at the Human Dimension in Artificial Intelligence Symposium held at the University of Kentucky (April 1988).     

Effect of Contact Residual Stress Relaxation on Fracture Strength of Indented Soda-Lime Glass

The strength of Vickers-indented soda-lime glass measured in air at room temperature steadily increases with time after indentation, whereas optical retardation steadily decreases in the same interval. Annealing after indentation causes further strength increase and retardation decrease. The results are consistent with Marshall and Lawn's treatment of the slow crack growth of indentation flaws driven by the combined influence of residual contact stress and applied stress. Post-indentation strengthening of indentation flaws can be explained without recourse to flaw blunting.     

Synthesis of Si3N4 with Emphasis on Si-S-N Chemistry

Industrial production of Si₃N₄ from SiCI₄, is increasing. An element rivaling CI in abundance and cheapness with potentially suitable chemistry for this application is sulfur. Thus, Si–S–N chemistry was investigated to determine its usefulness in producing Si₃N₄. Bifunctionality in S, as opposed to mono-functionality in CI, may allow special routes via polymers to become important.     

Segregation of Isovalent Impurity Cations at the Surfaces of MgO and CaO

Enthalpies of segregation for isovalent impurities in magnesium and calcium oxide as a function of surface concentration were calculated by using an atomistic computer simulation method. We have considered Be²⁺, Mg²⁺, Ca²⁺, Ba²⁺, and Ni²⁺, segregating to both (001) and (110) faces. The results obtained can be extrapolated to predict the behavior of other impurities including Mn²⁺, Fe²⁺, and Co²⁺, We find, for example, that Fe²⁺, Mn²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ will concentrate at the (001) surface of MgO, while Ni²⁺ will be depleted. The enthalpy of segregation is found to vary substantially with coverage particularly for the larger impurities. The enthalpy becomes less negative with increasing impurity concentration due to the increasing lattice strain until the surface is nearly saturated. Then additional stabilization is obtained by restructuring of the surface layer. We predict reconstructed surfaces for both the (001) and (110) faces, which contain a high concentration of a larger impurity ion. The enthalpy of segregation shows a maximum at around 50% surface coverage implying a bimodal surface distribution of segregant. The influence of segregation on surface energy suggests two unusual effects. The (001) surface energy of the impure crystal becomes negative for surface concentrations of impurity greater than 10% Ba²⁺ or 75% Sr²⁺ in MgO. This implies a thermodynamic barrier to sintering. At high coverages of Ba²⁺ in MgO the (110) surface becomes more stable than the (001) face suggesting that facetting may occur.     

Factors affecting cloud point analysis of palm oleins

Some of the factors affecting cloud point determination of palm oleins are described. These are the type of container used, method of stirring, rate of stirring and bath temperature. The repeatability and reproducibility standard deviations of the method are determined from collaborative trials. Recommendations for the test are made to reduce the large variations among laboratories.     

Stability studies on methyl and ethyl fatty acid esters of sunflowerseed oil

Fatty acid esters, high in linoleic acid, were prepared and stored for long-term engine tests. Storage tests with these esters were undertaken to obtain more information on optimal storage requirements and general stability characteristics. Samples were kept at three temperature levels (20 C, 30 C and fluctuating around 50 C) for a 90-day period and were removed at regular intervals for chemical and physical analysis. The influence of air, temperature, light, TBHQ and contact with mild steel was evaluated by comparing the free fatty acid, peroxide, anisidine, ultraviolet absorption, viscosity and induction periods. A statistical model was used to evaluate the data and to reduce the large number of data points to comparable curves. Storage of esters in contact with air, especially at a temperature above 30 C, resulted in significant increases in peroxide, ultraviolet absorption, free fatty acid, viscosity and anisidine values. Exclusion of air retarded oxidation at all temperature levels. A direct relationship between viscosity increases and oxidation parameters was evident. Exposure to light caused a small increase in the oxidation parameters of esters stored at the highest temperature level. Addition of TBHQ prevented oxidation of samples stored under moderate conditions. Under unfavorable storage conditions the anti-oxidant was no longer effective. Mild steel had very little effect on the oxidation parameters. Only the anisidine values of samples stored at the highest temperature level were slightly increased. Methyl esters performed slightly better than ethyl esters during the storage test. The following practical guidelines for storage of fatty acid ester fuels are: (i) airtight containers should be used; (ii) the storage temperature should be <30 C; (iii) mild steel (rust free) containers may be used, and (iv) TBHQ has a beneficial effect on oxidation stability.