Food anaphylaxis

    Figure Avoidance is the primary measure in food allergy confirmed

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Electromembrane extraction of peptides--fundamental studies on the supported liquid membrane

A large screening of different components in the supported liquid membrane (SLM) in electromembrane extraction (EME) was performed to test the extraction efficiency on eight model peptides. Electromembrane extraction from a 500 μL acidified aqueous sample containing the model peptides in the concentration 10 μg/mL was used. Extraction time was 5 min with an electric potential of 10 V and 900 rpm agitation of the sample vial. The samples were extracted through a hollow fiber-based SLM with different compositions of organic solvents and carriers. A small volume of acidified acceptor solution (25 μL) was after extraction analyzed directly, or with some dilution, on CE or HPLC. This article has identified mono- or di-substituted phosphate groups as the prominent group of carrier molecules needed to obtain acceptable recoveries. For the organic solvents, primary alcohols and ketones have shown promise regarding recovery and reproducibility, with some differences in selectivity. A new composition of the SLM, namely 2-octanone and tridecyl phosphate (90:10 w/w) has proved to give higher extraction recoveries and lower standard deviation than SLMs previously reported in the literature.     

Thermodynamic characterization of the binding of tetrahydropterins to phenylalanine hydroxylase

Phenylalanine hydroxylase (PAH) is the key enzyme in the catabolism of L-Phe. The natural cofactor of PAH, 6R-tetrahydrobiopterin (BH4), negatively regulates the enzyme activity in addition to being an essential cosubstrate for catalysis. The analogue 6-methyltetrahydropterin (6M-PH4) is effective in catalysis but does not regulate PAH. Here, the thermodynamics of binding of BH4 and 6M-PH4 to human PAH have been studied by isothermal titration calorimetry. At neutral pH and 25 degrees C, BH4 binds to PAH with higher affinity (Kd = 0.75 +/- 0.18 microM) than 6M-PH4 (Kd = 16.5 +/- 2.7 microM). While BH4 binding is a strongly exothermic process (DeltaH = -11.8 +/- 0.4 kcal/mol) accompanied by an entropic penalty (-TDeltaS = 3.4 +/- 0.4 kcal/mol), 6M-PH4 binding is both enthalpically (DeltaH = -3.3 +/- 0.3 kcal/mol) and entropically (-TDeltaS = -3.2 kcal/mol) driven. No significant changes in binding affinity were observed in the 5-35 degrees C temperature range for both pterins at neutral pH, but the enthalpic contribution increased with temperature rendering a heat capacity change (DeltaCp) of -357 +/- 26 cal/mol/K for BH4 and -63 +/- 12 cal/mol/K for 6M-PH4. Protons do not seem to be taken up or released upon pterin binding. Structure-based energetics calculations applied on the molecular dynamics simulated structures of the complexes suggest that in the case of BH4 binding, the conformational rearrangement of the N-terminal tail of PAH contribute with favorable enthalpic and unfavorable entropic contributions to the intrinsic thermodynamic parameters of binding. The entropic penalty is most probably associated to the reduction of conformational flexibility at the protein level and disappears for the L-Phe activated enzyme. The calculated energetic parameters aid to elucidate the molecular mechanism for cofactor recognition and the regulation of PAH by the dihydroxypropyl side chain of BH4.     

Language and Mathematics - Key Factors influencing the Comprehension Process in reality-based Tasks

Solving reality-based tasks is an important goal in mathematics instruction and is anchored in education standards determined by mathematical modeling skills. These tasks demand a serious examination of the real-world as well as text comprehension to successfully solve them. Therefore, this study empirically reconstructed the comprehension process during the solution of reality-based tasks and examined how it correlates with process-, person-, and task-related attributes. Fifty-five seventh graders using the Think Aloud Method solved reality-based tasks that were varied in their linguistic and situational complexity level. Their mathematical performance as well as their reading ability were measured. Based on detailed analyses of solution processes combined with the performance data, we point out the relevance of comprehension activities and empirically identify factors that influence the comprehension process.     

Developments in the Field of Inorganic Pigments

The specific properties of inorganic pigments result from an interplay of solid-state properties, particle size, and particle shape. However, phenomena occurring at the pigment interfaces also have implications for the use of the pigment. The interrelations for individual classes of pigments are indicated, and two selected examples, namely transparent colored pigments and magnetic pigments, are subsequently discussed with particular attention being paid to industrial developments.     

Synthesis,Electronic Properties and Reactivity of [B12X11(NO2)]2− (X=F–I) Dianions

Nitro-functionalized undecahalogenated closo-dodecaborates [B₁₂X₁₁(NO₂)]²⁻ were synthesized in high purities and characterized by NMR, IR, and Raman spectroscopy, single crystal X-diffraction, mass spectrometry, and gas-phase ion vibrational spectroscopy. The NO₂ substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B₁₂X₁₂]²⁻ (X=F–I) dianions evidenced by photoelectron spectroscopy, cyclic voltammetry, and quantum-chemical calculations. The stabilizing effect decreases from X=F to X=I. Thermogravimetric measurements of the salts indicate the loss of the nitric oxide radical (NO^.). The homolytic NO^. elimination from the dianion under very soft collisional excitation in gas-phase ion experiments results in the formation of the radical [B₁₂X₁₁O]^2−.. Theoretical investigations suggest that the loss of NO^. proceeds via the rearrangement product [B₁₂X₁₁(ONO)]²⁻. The O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formation by radical recombination of [B₁₂X₁₁O]^2−. and NO^. is demonstrated.     

Dynamic interactions and adsorption in systems of hydrophobically modified water-soluble polymers

Associating polymers are prepared from poly(oxyelliylene) and a diisocyanate and terminated by linear alcohols with 8 to 18 C-atoms. Solutions of these polymers in pure water and with surfactants have been investigated by dynamic light scattering and NMR self-diffusion. The diffusion results indicate that the polymers in solution form heterodisperse clusters that show a complex behavior of overlap and coupling to each other, a feature which may be described by the coupling theory of Ngai and coworkers. In addition competitive adsorption on polystyrene latex particle is measured and the results indicate a multilayer adsorption structure that is broken down by surfactant addition. Surfactant adsorption seems to be practically independent of adsorbed polymer, except for an “initial inhibition” concentration that may be connected to the desorption of secondary layers of adsorbed polymer.     

ChemInform Abstract: Infrared Spectroscopy of Hydrated Bicarbonate Anion Clusters: HCO3‐(H2O)1‐10.

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