Kinetic and thermodynamic acidities of substituted 1-benzyl-1-methoxy-2-nitroethylenes. Strong reduction of the transition state imbalance compared to other nitroalkanes

Acidity constants of six substituted 1-benzyl-1-methoxy-2-nitroethylenes (2-Z with Z = m-NO(2), m-CF(3), m-Cl, H, p-Me, p-MeO) and their respective nitronic acids were determined in 50% DMSO-50% water (v/v) at 20 degrees C. Kinetic data were obtained on the reversible deprotonation of all six 2-Z by OH(-) and piperidine and on the reversible deprotonation of 2-NO(2)() by piperazine, 1-(2-hydroxyethyl)piperazine, and morpholine in the same solvent. These data allowed a determination of the Br?nsted coefficients alpha (dependence on acidity of 2-Z) and beta (dependence on amine basicity). The fact that alpha > beta indicates the presence of a transition state imbalance which, however, is much smaller than that for the deprotonation of arylnitromethanes. The reasons for this reduction in the imbalance and their relevance to a recent study of the deprotonation of Fischer carbene complexes are discussed.     

Duality, thermodynamics, and the linear programming problem in constraint-based models of metabolism

It is shown that the dual to the linear programming problem that arises in constraint-based models of metabolism can be given a thermodynamic interpretation in which the shadow prices are chemical potential analogues, and the objective is to minimize free energy consumption given a free energy drain corresponding to growth. The interpretation is distinct from conventional nonequilibrium thermodynamics, although it does satisfy a minimum entropy production principle. It can be used to motivate extensions of constraint-based modeling, for example, to microbial ecosystems.     

Method development for the determination of iron in milligram amounts of rice plants (Oryza sativa L.) from cultivation experiments using graphite furnace atomic absorption spectrometry

The amount of sample that is available for analysis in laboratory plant cultivation experiments is usually very limited. Highly sensitive analytical techniques are therefore required, even for elements that are present in the plants at mg g^–1 concentrations, and graphite furnace atomic absorption spectrometry (GFAAS) was chosen in this work because of its micro-sampling capability, and its relatively simple operation. Four micro-methods were investigated for the determination of iron in roots and leaves of rice plants: i) a micro-digestion with nitric and hydrochloric acids, ii) a slurry procedure using tetramethylammonium hydroxide (TMAH) tissue solubilizer, iii) a slurry prepared in 1.4 mol L^–1 nitric acid, and treated in an ultrasonic bath, and iv) the direct analysis of solid samples. The micro-digestion was suffering from high blank values and contamination problems, so that it could not be recommended for routine purposes. The TMAH method exhibited poor precision and occasional low recoveries, particularly for real samples. Direct solid sampling analysis gave results similar to those obtained with the slurry technique with ultrasonic agitation for the determination of iron in certified reference materials with iron content up to about 100 g g^–1, but was too sensitive for the investigated rice plants, which had an iron content up to several mg g^–1. The slurry technique with ultrasonic treatment of the samples, suspended in dilute nitric acid, was finally adopted as the method of choice.The method was then applied for the determination of iron in the leaves and in different compartments of the roots of two rice cultivars, one sensitive to iron toxicity, an important nutritional disorder, and the other one resistant to iron toxicity. The results suggest that the higher resistance to iron toxicity of the second cultivar is due to a smaller uptake of iron from the soil, resulting in lower iron levels in all compartments of the plant.     

Finding Alignment: The Perceptions and Integration of the Next Generation Science Standards Practices by Elementary Teachers

Preparing elementary‐level teachers to teach in alignment with the eight Next Generation Science Standards (NGSS) practices could prove to be a daunting endeavor. However, the process may be catalyzed by leveraging elements of teacher science instruction that inherently attend to the practice standards. In this study, we investigated the science instruction of three grade 3–5 elementary‐level teachers. We used observation, interviews, and surveys to determine the level to which the teachers perceived they taught and engaged in teaching science aligned with the eight NGSS practices. We found that the teachers were partially, and intrinsically implementing several of these practices in their instruction, and at the same time could not articulate the eight NGSS practices. Our results suggest there may be ample opportunity to build on the current science instruction of elementary‐level teachers to bring their instruction into alignment with the NGSS. We found that teachers’ perceive professional development, school culture, and access to additional instructional resources to be essential to their adoption of the NGSS practices.     

Spectrographic determination of trace elements in cement

Summary A simple straight-forward spectrographic method is extended to the analysis of cement to cover elements of general interest to cement industry and to non-metallic materials. A d.c. arc of 9 amperes at 220 volts is used to determine the elements Mg, Sr, Ba, V, Nb, and Mn with reasonable detection limits using the visible region of the Hilger spectrograph. The sensitivity of the method is satisfactory and the precision is unusually good for a routine quantitative analysis.

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Zusammenfassung Obwohl im Schrifttum eine Reihe von Untersuchungen über die spektrochemische Bestimmung von Spurenelementen in Silicaten und Zement vorliegt, ergeben sich bei der praktischen Anwendung dieser Analysenvorschriften Schwierigkeiten.Im vorliegenden Verfahren war der Verzicht auf die Veraschung der Mischung der spektralanalytischen Proben mit Graphit deshalb notwendig, weil einige Elemente, wie z.B. Mg, Sr, Ba, V, Nb, Cr und Mn, auf direktem Weg im Zement quantitativ bestimmt werden. Die Nachweisempfindlichkeit beträgt etwa 10 ppm für die meisten Elemente mit einem mittleren Fehler von 3,0–8,0%.

     

Application of proteomics to hordein screening in the malting process

This study was undertaken to investigate the effect of the malting process on hordein composition. For this purpose, combination of sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and the method of isotopic peptides labeling iTRAQ was used. Barley proteins are essential components determining the quality of both malt and beer. Since hordeins represent the most abundant proteins accounting for about 40-50% of total protein fraction of mature barley grain, our research was focused on them. In this respect, the proteins of interest were extracted from milled samples of barley grain, germinated barley grain (samples collected at different time intervals), green malt and malt, respectively. Particular hordein extracts were firstly fractionated via SDS- PAGE, which was used as a relatively rapid and reliable technique providing information about hordein profile of analyzed samples. Then, separated proteins were in-gel digested and resulting peptides were measured by mass spectrometry. In addition, the chosen proteins, after in-gel digestion, were subjected to the iTRAQ method and the screening of proteins during malting process was evaluated. Our results have revealed that most of the hordein components present in the barley grain can be found in all stages of the malting process as well as in the final malt. The amount of hordeins decreases during the malting process; in the case of C hordein, the protein decrease is approximately 65%. On the other hand, significant degradation of D hordein was detected. The suggested procedure can be used to follow the development of the hordein profile during germination, which is of great technological importance in beer production.     

Use of calorimetry and thermal analysis to assess the heat of supplementary cementitious materials during the hydration of composite cementitious binders

Journal of Thermal Analysis and Calorimetry - The present paper focuses on the suitability, variability and versatility of thermal analysis and calorimetry methods in the study of cement hydration...     

Synthesis of heterocyclic compounds related to fredericamycin A – the cyclopent[g]isoquinoline system

A synthetic route is described to compounds 9 and 10 , which resemble the cyclopent[g]isoquinoline system of the antitumor agent, Fredericamycin A. The method is based upon directed lithiation of the pyridine 6 and conjugate addition to 2-cyclopenten-1-one. Cyclization of the product 7 with base then generates the required skeleton, which can be aromatized and methylated (7 → 8 → 9).     

Preparation of Novel,Functionalized 1,10-Phenanthrolines

The preparation of hydrophilic 2,9-dialkyl-1,10-phenanthrolines, including phenanthroline-5-sulfonic acids and phenanthrolines with side chain functionality is described. Nucleophilic aromatic substitution chemistry is used to obtain regiochemically defined phenanthroline sulfonic acids by much simpler means than have been available in the past.     

MALDI‐TOF mass spectrometry of hordeins: rapid approach for identification of malting barley varieties

A procedure for identification of malting barley varieties using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) of ethanol‐soluble barley proteins (hordeins) is described. The hordeins were first extracted from milled barley grains by several extraction protocols (using different extraction agents and conditions). Hordein extracts were then analyzed directly via MALDI‐TOF MS without any preliminary purification or separation step, and the protein profiles of analyzed hordein extracts were compared in order to find out the most suitable extraction procedure for mass spectrometric analysis. The optimized procedure was successfully applied to identification of 13 malting barley varieties. Our results revealed that the proposed mass spectrometry‐based approach provides characteristic mass patterns of extracted hordeins, which can be advantageously used for barley variety identification. Copyright © 2009 John Wiley & Sons, Ltd.