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.     

Is evidence-based practice diverse enough? Philosophy of science considerations.

In its policy rationale for evidence-based practice in psychology (EBPP), the APA Presidential Task Force on Evidence-Based Practice (see record 2006-05893-001) claims to have constituted itself with "scientists and practitioners from a wide range of perspectives and traditions, reflecting the diverse perspectives within the field" (p. 273). We applaud this attention to diversity but contend that an entire perspective of the debate was omitted in the Task Force's newly approved policy and its underlying report. The failure to consider a philosophy of science perspective led the Task Force to make a number of epistemological assumptions that are not based on evidence or rationale and that thus violate the very spirit of evidence-based decision making. In this comment, we reveal a few of these assumptions and discuss their detrimental consequences. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Contractor Prebid Planning Principles

Planning is an essential function of project management. Yet, many small- and medium-sized contractors do a relatively poor job of operational planning. Better prebid plans will reduce costs, shorten schedules, and improve labor productivity. Unfortunately, the published literature offers little guidance for smaller contractors on what constitutes effective planning. Most papers describe planning as a macrolevel process for owners. Most emphasize scope definition for industrial projects. This paper describes a microlevel planning process for contractors. It consists of eight steps which are: (1) assess contract risks; (2) develop a preliminary execution plan; (3) develop site layout plans; (4) identify the sequences that are essential-to-success; (5) develop detailed operational plans; (6) develop proactive strategies to assure construction input into design; (7) revise the preliminary plan; and (8) communicate and enforce the plan. The entire process is illustrated with a case study project and is fully illustrated with figures which show how to integrate the work of multiple contractors, keep key resources (crews or equipment) fully engaged with no downtime, provide time buffers so the work of follow on crews can be efficiently done, expedite the schedule using multiple work stations and concurrent work, ways to communicate the work plan to the superintendent and foremen, and how to assess the feasibility of various work methods. The steps are easy to understand and implement. They will yield immediate positive results.     

History of Construction, Engineering, and Management in the Department of Civil and Environmental Engineering at Penn State

At Penn State, the credit for broadening the Civil Engineering Department’s longstanding academic focus on analysis and design to include the construction phase must go to Dr. Harmer A. Weeden and his longtime associate Dr. Thomas D. Larson. Jack H. Willenbrock joined the Department as an Instructor in June 1968 and grew the construction program so that today about a fourth to a third of the civil undergraduates obtain employment in the construction industry. The program has awarded about 250 postbaccalaureate degrees.     

Model Selection in Applied Science and Engineering: A Decision-Theoretic Approach

Mathematical models are developed and used to study the properties of complex systems in just about every area of applied science and engineering. Information on the system being modeled is, in general, incomplete, so that there may be two or more models consistent with the available information. The collection of these models is called the class of candidate models. A decision-theoretic method is developed for selecting the optimal member from the collection. The optimal model depends on the available information, the class of candidate models, and the model use. The candidate models may be deterministic or random. Classical methods for model selection, including the method of maximum likelihood and Bayesian methods, are briefly reviewed. These methods ignore model use and require data to be available. In addition, examples are used to show that classical methods for model selection can be unreliable in the sense that they can deliver unsatisfactory models when data is limited. The proposed decision-theoretic method for model selection does not have these limitations. The method accounts for model use via a utility function. This feature is especially important when modeling high-risk systems where the consequences of using an inappropriate model for the system can be disastrous.     

Reminiscence: diffraction and the mountains of Alaska

Discusses, from a personal point of view, experiments carried out to study the diffraction and propagation of VHF, HF and MF radio waves in the early-mid 1950s in the mountains of Alaska     

System requirements for Ka-band Earth-satellite propagation data

Accurate estimates of the propagation impairments that affect link quality and availability and determine signal interference fields are essential for the reliable design of telecommunication systems and the efficient use of the electromagnetic spectrum. Recent announcements by commercial entities of their intent to use Ka-band spectrum to supply satellite services have heightened interest in propagation data and models for these frequencies. This paper provides a brief overview of Ka-band Earth-satellite systems and requirements in relation to the need for specific types of propagation data     

Four state binary QAM trellis code better than known codes

Presents a new one-memory quaternary four-state trellis code, and its four-state binary equivalent code based on a QAM constellation which is 0.52 dB better than the four-state Ungerboeck code.<>     

Adiabatic couplers: design rules and optimization

Explicit analytic design rules are derived for both 3 dB and full adiabatic couplers. The design rules are in excellent agreement with numerical calculations using the beam propagation method (BPM). It is shown that the length scaling for 3 dB couplers compared to full couplers makes the former more difficult to design. The design for each case is optimized to obtain the upper limit of performance and a comparison is carried out between two different design geometries for both 3 dB and full adiabatic couplers     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.