Role of the Protein Cavity in Phytochrome Chromoprotein Assembly and Double-bond Isomerization: A Comparison with Model Compounds

Difference patterns of ¹³C NMR chemicals shifts for the protonation of a free model compound in organic solution, as reported in the literature (M. Stanek, K. Grubmayr [1998] Chem. Eur. J. 4 , 1653–1659), were compared with changes in the protonation state occurring during holophytochrome assembly from phycocyanobilin (PCB) and the apoprotein. Both processes induce identical changes in the NMR signals, indicating that the assembly process is linked to protonation of the chromophore, yielding a cationic cofactor in a heterogeneous, quasi-liquid protein environment. The identity of both difference patterns implies that the protonation of a model compound in solution causes a partial stretching of the geometry of the macrocycle as found in the protein. In fact, the similarity of the difference pattern within the bilin family for identical chemical transformations represents a basis for future theoretical analysis. On the other hand, the change of the ¹³C NMR chemical shift pattern upon the Pr → Pfr photoisomerization is very different to that of the free model compound upon ZZZ → ZZE photoisomerization. Hence, the character of the double-bond isomerization in phytochrome is essentially different from that of a classical photoinduced double-bond isomerization, emphasizing the role of the protein environment in the modulation of this light-induced process.     

High‐School Students' Approaches to Solving Algebra Problems that are Posed Symbolically: Results from an Interview Study

A cross‐curricular structured‐probe task‐based clinical interview study with 44 pairs of third year high‐school mathematics students, most of whom were high achieving, was conducted to investigate their approaches to a variety of algebra problems. This paper presents results from three problems that were posed in symbolic form. Two problems are TIMSS items (a linear inequality and an equation involving square roots). The other problem involves square roots. We found that the majority of student pairs used symbol manipulation when solving the problems, and while many students seemed to prefer symbolic over graphical and tabular representations in their first attempt at solving the problems, we found that it was common for student pairs to use more than one strategy throughout the course of their solving. Students' use of graphing calculators to solve the problems is discussed.     

Possible effects on the polyethene chain structure of trimethylaluminum coordination to zirconocene catalysts

Ethene was polymerized with the catalytic systems L₂ZrCl₂/MAO/TMA (where L = Cp, Me₅Cp, or Me₄Cp; Cp = η⁵‐cyclopentadienyl; MAO = methylaluminoxane; and TMA = trimethylaluminum) at 60 °C, 2 bar, and Al_TMA/Zr ratios of 0–2700. The polymerization activity was reduced with the addition of TMA for L = Cp but was almost unaffected for the methyl‐substituted catalysts. Increasing the TMA concentration resulted in a lower molecular weight of the polymer, with the largest effect for L = Me₅Cp. A gel permeation chromatography analysis of the polymers revealed a high molecular weight shoulder and a nearly bimodal distribution for L = Me₅Cp at high TMA concentrations. A possible explanation of such a shoulder in terms of long‐chain branching was ruled out by dynamic viscosity measurements. The origin of this effect more likely stemmed from competition between chain transfer to aluminum and β‐hydrogen transfer reactions at two different sites, one TMA‐sensitive and one TMA‐insensitive. Polymerizations at various pressures and temperatures substantiated this assumption. A clue to the underlying mechanism came from investigations of chain transfer to TMA studied with density functional calculations. Complexation of Me₃Al to Zr was much stronger for L = Cp than for L = Me₅Cp. However, the overall chain‐transfer barrier was much higher for L = Cp. These results agreed both with the reduced activity for L = Cp and with the strongly reduced molecular weight for L = Me₅Cp observed with the addition of TMA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3566–3577, 2001     

Natural dissolved organic matter affects electrospray ionization during analysis of emerging contaminants by mass spectrometry

Dissolved organic matter (DOM), present in many forms in water, can interfere with analysis of organic contaminants by atmospheric pressure ionization–mass spectrometry. A quantitative analysis of this interference, or matrix effect, on organic contaminant target analyte measurements was carried out using un-fractionated and fractionated dissolved natural organic matter from the Suwannee River, GA (SROM), a standard reference material, that was directly infused into the tandem mass spectrometer during multiple reaction monitoring (MRM) of a suite of endocrine disrupting compounds–pharmaceuticals and personal care products (EDC/PPCPs). Most target analytes suffered signal suppression in the presence of both fractionated and un-fractionated SROM, however greater interferences were measured with fractionated relative to bulk SROM. This finding is consistent with the view of organic matter as a supramolecular association of low molecular mass components having separate charged and structural features revealed only after dissociation.     

Electronic structure of the water oxidation catalyst cis,cis-[(bpy)2(H2O)Ru(III)ORu(III)(OH2)(bpy)2]4+, the blue dimer

The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru(III) ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK(a) values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru(III) appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ(1)*)(2) with a low-lying, paramagnetic triplet state (dπ(1)*)(1)(dπ(2)*)(1). Systematic structural-magnetic-IR correlations are observed between ν(sym)(RuORu) and ν(asym)(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with ∠Ru-O-Ru dictated by the distortion and electron-electron repulsion.     

Torch Design Modification Using Micro-jets to Suppress Fluid Dynamic Instabilities in Plasma Arc Cutting

Highly constricted plasma arcs are widely used for metal cutting. One important characteristic of the cutting process is the consistency of the cut edge around the perimeter of the workpiece. Cut edge properties, including surface roughness, edge shape and dross formation, are presumed to depend on the local temperature and chemical composition of the cutting arc adjacent to the cut edge. Fluid dynamic instabilities in the arc boundary leading to entrainment of the low temperature ambient gas can have a strong effect on cutting performance. This paper describes the use of micro-jets to suppress fluid dynamic instabilities in the boundary layer of a plasma cutting arc. Previously developed optical diagnostics and analysis methods are used to characterize the arc boundary layer. Multiple nozzle designs have been investigated to quantify the effects of utilizing micro-jet flow around the arc column, and some relationships between nozzle design and cut quality are presented.     

Molecular interactions in biofilms

A biofilm may be defined as a microbially derived, sessile community characterized by cells that attach to an interface, embed in a matrix of exopolysaccharide, and demonstrate an altered phenotype. This review covers the current understanding of the nature of biofilms and the impact that molecular interactions may have on biofilm development and phenotype using the motile gram-negative rod Pseudomonas aeruginosa and the nonmotile gram-positive cocci Staphylococcus aureus as examples.     

Endotrivial modules for the general linear group in a nondefining characteristic

Suppose that \(G\) is a finite group such that \(\mathrm{SL }(n,q)\subseteq G \subseteq \mathrm{GL }(n,q)\), and that \(Z\) is a central subgroup of \(G\). Let \(T(G/Z)\) be the abelian group of equivalence classes of endotrivial \(k(G/Z)\)-modules, where \(k\) is an algebraically closed field of characteristic \(p\) not dividing \(q\). We show that the torsion free rank of \(T(G/Z)\) is at most one, and we determine \(T(G/Z)\) in the case that the Sylow \(p\)-subgroup of \(G\) is abelian and nontrivial. The proofs for the torsion subgroup of \(T(G/Z)\) use the theory of Young modules for \(\mathrm{GL }(n,q)\) and a new method due to Balmer for computing the kernel of restrictions in the group of endotrivial modules.