Mechanistic pathways of the hydroxyl radical reactions of quinoline. 1. Identification, distribution, and yields of hydroxylated products

The mechanistic details of the hydroxyl radical-induced transformations of quinoline have been elucidated. The nature and distribution of the final products have provided insight into the preferential attack of the hydroxyl radicals at different sites on the aromatic rings. Hydroxylated products at all of the carbon atoms but one, C2, have been observed and quantified following controlled radiolysis of N2O-purged aqueous quinoline solutions. The difference in the growth pattern and the lifetime of the monohydroxylated products under radiolytic conditions, as well as the formation of high-molecular-weight products (e.g., quinoline dimers), shows the complexity of the OH reaction pathways. The radiolytic yields (G values) for the degradation of the quinoline and the formation of the hydroxylated products are calculated in the absence and in the presence of an oxidant, K3Fe(CN)6. The addition of K3Fe(CN)6 changes only the distribution of the hydroxylated products. These experiments indicate that the nature of the hydroxylated products is determined in the initial addition step of the reaction of the hydroxyl radical with quinoline, whereas the chemistry of the OH adducts is relevant to the distribution of the final products. The discrepancy between the products of -radiolysis and the photo-Fenton reaction of quinoline is also discussed.     

Effect of dopant on the physical properties of polymer films for microphotonics

This paper presents experimental results concerning the influence of the additives on the physical properties of polymer films. Metal oxides/inorganic salts were used as additives in vinyl-polymers solutions. The physical properties of the metal doped polymer films can be significantly modified by the composition of the doping elements and the curing conditions of the polymer. Morphologic, electronic, magnetic and optic properties of the doped polymers were analysed by AFM, SEM, Mössbauer spectroscopy and optical measurements. The film composition and the deposition processes were optimized to allow a better control of the optical parameters (refractive index, transmission), to reduce the processing temperatures and to improve the chemical sensitivity of the films for sensor applications. These compounds can be easily spin coated onto a variety of directly patterned semiconductor substrates.     

Influence of nitroxide structure on polystyrene brushes “grafted‐from” silicon wafers

Alkoxyamine derivatives based on 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO), N‐tert‐butyl‐N‐(1‐diethylphosphono‐(2,2‐dimethylpropyl)) nitroxide (SG1) and N‐tert‐butyl‐N‐(2‐methyl‐1‐phenylpropyl) nitroxide (TIPNO) containing a C₁₁ hydrophobic spacer and a reactive triethoxysilyl polar head, were synthesized and anchored to silicon wafers by the Langmuir–Blodgett reactive deposition technique at surface pressures ranging from 15 to 32 mN/m. Polystyrene brushes (M_n ～ 8500–66,400 g/mol) were grown from the alkoxyamine functionalized silicon wafers by nitroxide mediated radical polymerization and characterized by ellipsometry and water contact angle measurements. The main parameters influencing the grafting density and the degree of stretching of the brushes are the nitroxide polarity and, therefore, the behavior of the corresponding alkoxyamines at the air/water interface of the Langmuir–Blodgett trough. Depending on the alkoxyamine chemical structure and the surface pressure during Langmuir–Blodgett deposition, polystyrene brushes with grafting densities of 0.3–1.0 chains/nm² and stretching values of 40–70% were obtained. Regarding alkoxyamines deposited at high surface pressures, size exclusion chromatography experiments performed on both cleaved polystyrene brushes and chains simultaneously grown in the bulk revealed that the polymerization degree of the bulk and surface chains are significantly different, suggesting that steric constrains affect the polymerization kinetics occurring at the silicon surface. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3367–3374, 2008     

Polygonal chains cannot lock in 4D

We prove that, in all dimensions d4, every simple open polygonal chain and every tree may be straightened, and every simple closed polygonal chain may be convexified. These reconfigurations can be achieved by algorithms that use polynomial time in the number of vertices, and result in a polynomial number of “moves”. These results contrast to those known for d=2, where trees can “lock”, and for d=3, where open and closed chains can lock.     

The Influence of Adnectin Binding on the Extracellular Domain of Epidermal Growth Factor Receptor

The precise and unambiguous elucidation and characterization of interactions between a high affinity recognition entity and its cognate protein provides important insights for the design and development of drugs with optimized properties and efficacy. In oncology, one important target protein has been shown to be the epidermal growth factor receptor (EGFR) through the development of therapeutic anticancer antibodies that are selective inhibitors of EGFR activity. More recently, smaller protein derived from the 10th type III domain of human fibronectin termed an adnectin has also been shown to inhibit EGFR in clinical studies. The mechanism of EGFR inhibition by either an adnectin or an antibody results from specific binding of the high affinity protein to the extracellular portion of EGFR (exEGFR) in a manner that prevents phosphorylation of the intracellular kinase domain of the receptor and thereby blocks intracellular signaling. Here, the structural changes induced upon binding were studied by probing the solution conformations of full length exEGFR alone and bound to a cognate adnectin through hydrogen/deuterium exchange mass spectrometry (HDX MS). The effects of binding in solution were identified and compared with the structure of a bound complex determined by X-ray crystallography. ?      

Ion mobility adds an additional dimension to mass spectrometric analysis of solution-phase hydrogen/deuterium exchange

The goal of this study was to determine the utility of adding ion mobility spectrometry to studies probing the solution-phase hydrogen/deuterium exchange (HX) of proteins. The HX profile of the Hck SH3 domain was measured at both the intact protein and the peptic peptide levels in the Waters Synapt HDMS system which uses a traveling wave to accomplish ion mobility separation prior to time-of-flight (Tof) m/z analysis. The results indicated a similar loss of deuterium with or without use of mobility in the Synapt and a level of deuterium loss comparable with a non-mobility Q-Tof instrument. The drift time of this small protein and its peptic peptides did not noticeably change due to solution-based deuterium incorporation. Importantly, ion mobility separations provided an orthogonal dimension of separation in addition to the reversed-phase high-performance liquid chromatography (RP-HPLC). The additional dimension of separation allowed for the deconvolution of overlapping isotopic patterns for co-eluting peptides and extraction of valuable deuterium incorporation data for those peptides. Taken together, these results indicate that including ion mobility separation in HX MS analyses further improves the mass spectrometry portion of such experiments. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Hypervalent organobismuth(iii) carbonate, chalcogenides and halides with the pendant arm ligands 2-(Me2NCH2)C6H4 and 2,6-(Me2NCH2)2C6H3

R2BiOH (1) [R = 2-(Me2NCH2)C6H4] and (R2Bi)2O (2) are formed by hydrolysis of R2BiCl with KOH. Single crystals of were obtained by air oxidation of (R2Bi)2. The reaction of R2BiCl and Na2CO3 leads to (R2Bi)2CO3 (3). 3 is also formed by the absorption of CO2 from the air in solutions of 1 or 2 in diethyl ether or toluene. (R2Bi)2S (4) is obtained from R2BiCl and Na2S or from (R2Bi)2 and S8. Exchange reactions between R2BiCl and KBr or NaI give R2BiX [X = Br (5), I (6)]. The reaction of RBiCl2 (7) with Na2S and [W(CO)5(THF)] gives cyclo-(RBiS)2[W(CO)5]2 (8). cyclo-(R'BiS)2 (9) [R' = 2,6-(Me2NCH2)2C6H3] is formed by reaction of R'BiCl2 and Na2S. The structures of were determined by single-crystal X-ray diffraction.     

Demystification of the geometric Fourier transforms and resulting convolution theorems

T. Qian As it will turn out in this paper, the recent hype about most of the Clifford–Fourier transforms is not thoroughly worth the pain. Almost everyone that has a real application is separable, and these transforms can be decomposed into a sum of real valued transforms with constant multivecor factors. This fact makes their interpretation, their analysis, and their implementation almost trivial. Copyright © 2015 John Wiley & Sons, Ltd.