Hydrogen Bond Compression during Triple Proton Transfer in Crystalline Pyrazoles. A Dynamic 15N NMR Study

Using dynamic solid state ¹⁵N CPMAS NMR spectroscopy (CP ≡ cross polarization, MAS ≡ magic-angle spinning), the kinetics of degenerate intermolecular triple proton and deuteron transfers in the cyclic trimers of ¹⁵N-labeled polycrystalline 4-nitropyrazole (4NO₂P) and 4-bromopyrazole (4BrP) have been studied as a function of temperature and are compared to the kinetics of triple proton transfer in bulk solid 3,5-dimethylpyrazole (DMP) studied previously. The results show that the transfer kinetics in the new trimers are much faster than in DMP. However, the kinetic HHH/HHD/HDD/DDD isotope effects of 4NO₂P are similar to those of DMP. These effects indicate a single barrier for the triple proton transfers where all three protons lose zero-point energy in the transition state, as expected for a structure with three compressed hydrogen bonds. At low temperatures, strong deviations from an Arrhenius-behavior are observed which are described in terms of a modified Bell tunneling model and a concerted proton motion. The barrier for the triple proton transfer in 4NO₂P and 4BrP is substantially smaller than in DMP. As there is no correlation with the electronic properties of the substituents, we assign this finding to steric effects where the bulky methyl groups of DMP in the 3- and 5-positions hinder the hydrogen bond compression, in contrast to 4NO₂P and 4BrP exhibiting substitutents in the 4-position. These results lead to a minimum energy pathway of the proton transfer following in the absence of steric hindering the hydrogen bond correlation line q₁ = f(q₂), established previously, where q₁ represents the deviation of the proton from the hydrogen bond center and q₂ the N…N distance. Tunneling occurs at constant N…N distances.     

A Microeconomic Perspective on Water Resources Management: Analyzing the Effects on Optimal Land Rents Along a River Basin

Water scarcity is becoming an increasingly relevant issue in many regions of the world as demand for water continues to grow. As a result, the need for finding measures that efficiently allocate increasingly scarce water resources has become a primary topic on the agendas of many water resource management authorities. This paper presents an innovative approach that provides further insight into the connection between hydrological, environmental, and economic aspects along a river basin. In short, it analyzes how land rents along a river basin are affected by managing water pollution along a river basin, given certain hydrological characteristics of the river basin. Results show that, without the implementation of a water management system to control water quality, the negative external effects of upstream water discharges on downstream locations can be internalized through a decrease in downstream land rents. However, the analysis presented in this paper also reveals that it is not only the absence or the presence of a water management system that has a significant impact on the real estate market along the river basin. Moreover, the market outcome also varies with the type of water resources management system implemented.     

Low‐Cost Post‐Growth Treatments of Crystalline Silicon Nanoparticles Improving Surface and Electronic Properties

Freestanding silicon nanocrystals (Si‐ncs) offer unique optical and electronic properties for new photovoltaic, thermoelectric, and other electronic devices. A method to fabricate Si‐ncs which is scalable to industrial usage has been developed in recent years. However, barriers to the widespread utilization of these nanocrystals are the presence of charge‐trapping defects and an oxide shell formed upon ambient atmosphere exposure hindering the charge transport. Here, we exploit low‐cost post‐growth treatment routes based on wet‐etching in hydrofluoric acid plus surface hydrosilylation or annealing enabling a complete native oxide removal and a reduction of the defect density by up to two orders of magnitude. Moreover, when compared with only H‐terminated Si‐ncs we report an enhancement of the conductivity by up to a factor of 400 for films of HF etched and annealed Si‐ncs, which retain a defect density below that of untreated Si‐ncs even after several months of air exposure. Further, we demonstrate that HF etched and hydrosilylated Si‐ncs are extremely stable against oxidation and maintain a very low defect density after a long‐term storage in air, opening the possibility of device processing in ambient atmosphere.     

Photo‐crosslinking of poly[ethene‐stat‐(methacrylic acid)] functionalised with maleimide side groups

BACKGROUND: Photo‐crosslinkable polymers are well known and commercially applied as photoresists. But so far they have not been applied as membrane materials for separation processes. They would offer certain advantages in membrane fabrication over conventional crosslinked polymer materials. Therefore, in this work, a poly[ethene‐stat‐(methacrylic acid)] (PEMAA) which is a potential membrane polymer for different separation problems was functionalised with photo‐crosslinkable maleimide side groups. RESULTS: It has been shown that PEMAA can be used as basic polymer material and a conversion with 3‐hydroxypropylmaleimide is possible in order to obtain a photo‐crosslinkable polymer. Investigation of the crosslinking mechanism was performed using stationary infrared and UV‐visible spectroscopy as well as nanosecond transient spectroscopy absorption measurements of a rotating film. Intense transient absorption of the maleimide‐esterified PEMAA occurs at 250 nm in the film pointing to maleimide anion formation and crosslinking via an ionic dimerisation mechanism. CONCLUSION: It is found that crosslinking reactions can be observed spectroscopically in situ using a maleimide‐functionalised PEMAA. Furthermore, experiments can be performed in the liquid phase (polymer in solution) as well as in the solid phase (polymer film) using a rotating polymer film sample. Maleimide anion formation and crosslinking via an ionic dimerisation mechanism can be investigated by variation of the polymer structure as well as the structure of the maleimide side groups. Copyright © 2009 Society of Chemical Industry     

A Comparison of the Rough Sets and Recursive Partitioning Induction Approaches: An Application to Commercial Loans

Credit scoring is the term used to describe methods utilized for classifying applicants for credit into classes of risk. This paper evaluates two induction approaches, rough sets and decision trees, as techniques for classifying credit (business) applicants. Inductive learning methods, like rough sets and decision trees, have a better knowledge representational structure than neural networks or statistical procedures because they can be used to derive production rules. If decision trees have already been used for credit granting, the rough sets approach is rarely utilized in this domain. In this paper, we use production rules obtained on a sample of 1102 business loans in order to compare the classification abilities of the two techniques. We show that decision trees obtain better results with 87.5% of good classifications with a pruned tree, against 76.7% for rough sets. However, decision trees make more type–II errors than rough sets, but fewer type–I errors.     

Education reform: Challenges for psychology and psychologists.

National, state, and local education reform agendas have been on a fast track for more than a decade. Although some psychologists have been active in promoting psychology and psychological services in education reform initiatives, knowledge about their efforts is fragmented. In order to educate psychologists about education reform, this article highlights the impetus for the recent education reform movement, briefly reviews the latest waves of education reform, and discusses the development of the National Education Goals. Then, an argument is made for the integration of education, health, and social reform initiatives; state-level education reform principles and initiatives are highlighted, illustrated by the systemic education reform mandate in Kentucky. Next, progress toward the development and implementation of an APA-sponsored response to the National Education Goals is discussed. Finally, objectives and roles for psychologists in advancing education reform are presented, and guidelines for the education and training of future psychologists are introduced. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Examination of the mediational influences of peer norms, environmental influences, and parent communications on heavy drinking in athletes and nonathletes.

The present study used perspectives from the general literature on college alcohol consumption to examine mediational influences of peer, environmental, and parental variables on heavy drinking for student athlete and nonathlete samples. Eight hundred thirty-five freshmen who differed in organized sports involvement were compared on heavy drinking outcomes, peer norms, environmental influences, and parental communication. College athletes reported significantly more heavy drinking experiences than nonathletes. Peer norms, environmental influences, and parental communication were all significant mediators of the athlete-heavy drinking relationship. Athletes reported a higher perception of peer drinking, peer approval of drinking, higher alcohol availability, and direct drink offers, which, in turn, were related to higher rates of heavy drinking. Parental communication mediated the athlete-heavy drinking relationship differently, depending on the specific topic of conversation. Discussion surrounding the importance of incorporating a variety of interventions aimed at reducing collegiate athlete drinking on the basis of the peer, environmental, and parental influences observed in the present analyses are presented. Limitations and directions for future research are also noted. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

An Efficient Sequential Optimization Approach Based on the Multivariate Expected Improvement Criterion

An efficient sequential optimization approach for complex computer models was presented by Jones et al. (1998). After fitting a stochastic process model based on an initial space filling design, this model is sequentially refined by the expected improvement criterion. This criterion balances the need to search in areas in the design space where the prediction is optimal with the need to search where the model uncertainty is high. This approach can easily be extended to physical processes. Since in practice the overall quality of products of production processes is assessed by more than one response, a multivariate version of the expected improvement criterion is proposed based on desirability functions. This criterion is then used to optimize a metal spinning process.     

Temporal information processing and pitch discrimination as predictors of general intelligence.

In the present study, the relationship between performance on temporal and pitch discrimination and psychometric intelligence was investigated in a sample of 164 participants by means of an experimental dissociation paradigm. Performance on both temporal and pitch discrimination was substantially related to psychometric intelligence (r = .43 and r =.39). Regression analysis and structural equation modeling suggested that both psychophysical domains can be considered as valid predictors of psychometric intelligence. Both predictor variables contributed substantial portions of both shared and unique variance to the prediction of individual differences in psychometric intelligence. Thus, the present study yielded further evidence for a functional relationship between psychometric intelligence and temporal as well as pitch discrimination acuity. Eventually, findings are consistent with the notion that temporal discrimination - in addition to general aspects of sensory discrimination shared with pitch discrimination - reflects specific intelligence-related aspects of neural information processing. (PsycINFO Database Record (c) 2010 APA, all rights reserved)