Deliberately Losing Control of C−H Activation Processes in the Design of Small-Molecule-Fragment Arrays Targeting Peroxisomal Metabolism

Combined photochemical arylation, “nuisance effect” (S_NAr) reaction sequences have been employed in the design of small arrays for immediate deployment in medium-throughput X-ray protein–ligand structure determination. Reactions were deliberately allowed to run “out of control” in terms of selectivity; for example the ortho-arylation of 2-phenylpyridine gave five products resulting from mono- and bisarylations combined with S_NAr processes. As a result, a number of crystallographic hits against NUDT7, a key peroxisomal CoA ester hydrolase, have been identified.     

Reactive Element Effects in High-Temperature Alloys Disentangled

Reactive elements—REs—are decisive for the longevity of high-temperature alloys. This work joins several previous efforts to disentangle various RE effects in order to explain apparently contradicting experimental observations in alumina forming alloys. At 800–1000 °C, “messy” aluminum oxy-hydroxy-hydride transients initially formed due to oxidation by H₂O which in turn undergo secondary oxidation by O₂. The formation of the transient oxide becomes supported by dispersed RE oxide particles acting as water equivalents. At higher temperatures, electron conductivity in impurity states owing to oxygen vacancies in grain boundaries (GBs) becomes increasingly relevant. These channels are subsequently closed by REs pinning the said vacancies. The universality of the emerging understanding is supported by a comparative first-principles study by means of density functional theory addressing RE(III): Sc₂O₃, Y₂O₃, and La₂O₃, and RE(IV): TiO₂, ZrO₂, and HfO_2, that upon reaction with water, co-decorate a generic GB model by hydroxide and RE ions. At 100% RE coverage, the GB model becomes relevant at both temperature regimes. Based on reaction enthalpy ΔH_r considerations, “messy” aluminum oxy-hydroxy-hydride transients are accessed in both classes. Larger variations in ΔH_r are found for RE(III)-decorated alumina GBs as compared to RE(IV). For RE(III), correlation with GB width is found, increasing with increased ionic radius. Similarly, upon varying RE(IV), minor changes in stability correlate with minor structural variations. GB decorations by Ce(III) and Ce(IV) further consolidate the emerging understanding. The findings are used to discuss experimental observations that include impact of co-doping by RE(III) and RE(IV).

     

Rheological behavior of neat and carbon fiber-reinforced poly(ether ketone ketone) for extrusion deposition additive manufacturing

To develop new materials for extrusion additive manufacturing (AM) systems, a fundamental understanding of rheological properties is essential to correlate the effect of processing on material structure and its properties. In this work, the rheological properties of five different grades of neat and carbon fiber (CF)-reinforced poly(ether ketone ketone) are reported. Rheological properties are essential to understand the effect of reinforcing fibers and AM process parameters such as time, temperature, environment, and shear rate on flow behavior during processing. Small-amplitude oscillatory shear tests and steady shear tests indicated neat grades to exhibit less increase in viscosity over time when processed in air than the CF-filled grades. The filled grades showed greater shear thinning and lower sensitivity to temperature. Overall, this rheological analysis provides a broad framework for determining appropriate processing conditions for extrusion deposition AM of such high-temperature polymer systems.     

Solutions to a combined problem of excessive hydrogen sulfide in biogas and struvite scaling.

The Woodman Point Wastewater Treatment Plant (WWTP) in Western Australia has experienced two separate problems causing avoidable maintenance costs: the build-up of massive struvite (MgNH4PO4. 6H2O) scaling downstream of the anaerobic digester and the formation of hydrogen sulfide (H2S) levels in the digester gas to levels that compromised gas engine operation and caused high operating costs on the gas scrubber. As both problems hang together with a chemical imbalance in the anaerobic digester, we decided to investigate whether both problems could be (feasibly and economically) addressed by a common solution (such as dosing of iron solutions to precipitate both sulfide and phosphate), or by using separate approaches. Laboratory results showed that, the hydrogen sulfide emission in digesters could be effectively and economically controlled by the addition of iron dosing. Slightly higher than the theoretical value of 1.5 mol of FeCl3 was required to precipitate 1 mol of dissolved sulfide inside the digester. Due to the high concentration of PO4(3-) in the digested sludge liquor, significantly higher iron is required for struvite precipitation. Iron dosing did not appear an economic solution for struvite control via iron phosphate formation. By taking advantage of the natural tendency of struvite formation in the digester liquid, it is possible to reduce the risk of struvite precipitation in and around the sludge-dewatering centrifuge by increasing the pH to precipitate struvite out before passing through the centrifuge. However, as the Mg2+/PO4(3-) molar ratio in digested sludge was low, by increasing the pH alone (using NaOH) the precipitation of PO4(3-) was limited by the amount of cations (Ca2+ and Mg2+) available in the sludge. Although this would reduce struvite precipitation in the centrifuge, it could not significantly reduce PO4(3-) recycling back to the plant. For long-term operation, maximum PO4(3-) reduction should be the ultimate aim to minimise PO4(3-) accumulation in the plant. Magnesium hydroxide liquid (MHL) was found to be the most cost-effective chemical to achieve this goal. It enhanced struvite precipitation from both, digested sludge and centrate to the point where more than 95% PO4(3-) reduction in the digested sludge was achieved.     

Preschool Competency in Context: An Investigation of the Unique Contribution of Child Competencies to Early Academic Success.

The present concurrent study combined developmental and ecological considerations to examine the unique contribution of multiple preschool competencies to an indicator of early academic success. Participants included 195 Head Start children from 32 classrooms representative of a large, urban Head Start program. Dimensional (variable-centered) analyses revealed 3 distinct classroom competency dimensions (i.e., General Classroom Competencies, Specific Approaches to Learning, and Interpersonal Classroom Behavioral Problems). The first 2 of these dimensions were found to be uniquely associated with early academic success. Findings from typological (person-centered) analyses supported the dimensional findings. Typological analyses revealed 7 profiles of classroom competency distinguished by high scores on the dimensions of General Competencies and Approaches to Learning, and these profiles were found to relate differentially to the indicator of early academic success. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

PARTNERS IN EXCELLENCE Metrics and Productivity Programs

For many companies, productivity improvements are the watchwords of the 1990s. IS organizations are having to demonstrate increased productivity on an annual basis. For the end-user computing (EUC) department, this requirement often comes in addition to the request to quantify the services it provides, presenting the EUC manager with the proverbial nightmare of juggling two number-one priorities. Which should receive the highest attention? The savvy manager recognizes that the correct answer is both.     

What results when firms implement practices: The differential relationship between specific practices, firm financial performance, customer service, and quality.

Previous research on organizational practices is replete with contradictory evidence regarding their effects. Here, the authors argue that these contradictory findings may have occurred because researchers have often examined complex practice combinations and have failed to investigate a broad variety of firm-level outcomes. Thus, past research may obscure important differential effects of specific practices on specific firm-level outcomes. Extending this research, the authors develop hypotheses about the effects of practices that (a) enable information sharing, (b) set boundaries, and (c) enable teams on 3 different firm-level outcomes: financial performance, customer service, and quality. Relationships are tested in a sample of observations from over 200 Fortune 1000 firms. Results indicate that information-sharing practices were positively related to financial performance 1 year following implementation of the practices, boundary-setting practices were positively related to firm-level customer service, and team-enabling practices were related to firm-level quality. No single set of practices predicted all 3 firm-level outcomes, indicating practice-specific effects. These findings help resolve the theoretical tension in the literature regarding the effects of organizational practices and offer guidance as to how to best target practices to increase specific work-related outcomes. Implications for theory, research, and practice are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Juvenile mood disorders and office psychopharmacology

Mood disorders afflict pediatric patients, cause significant impairment, and interfere with normal development. Increasingly, pediatricians are called on to assess and collaborate with mental health practitioners in medicating children and adolescents with mood disorders. Approaching the juvenile with a primary emphasis on clarifying the diagnoses, determining environmental antecedents and sequelae, and investigating suicide risk enables the pediatrician to institute appropriate treatment. Despite limited data from controlled studies, psychotherapy often is used for mild to moderate depression. Pharmacotherapy is indicated in cases unresponsive to psychotherapy and in severe or suicidal cases. First-line pharmacotherapy for depressed adolescents is usually an SRI followed by the atypical or TCA antidepressants. Bipolar disorder typically requires an aggressive medication regimen, including anticonvulsants, lithium, or a combination, as well as environmental modifications. With severe, difficult, or refractory cases, mental health consultation is recommended to clarify diagnoses and to provide psychotherapy and medication input.