Poly?thylenoxidverbindungen

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Interface engineering of photoelectrochemically prepared Si surfaces

The oxide of Si(1 1 1) formed by electropolishing in dilute ammonium fluoride solution is analysed by photoelectron spectroscopy using synchrotron radiation. The oxidic layer is about 3.1 nm thick and contains Si-F_x species as well as oxyfluorides. The oxyfluorides are found preferentially at the electropolishing layer surface. SiOH species are concentrated at the oxidic film/substrate interface. The full width half maximum of the Si 2p line indicates that the Si/electropolishing oxide interface is smoother than the Si/natural oxide interface.     

Reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in suspension

The reversible addition–fragmentation chain transfer polymerization of methyl methacrylate mediated by 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB) in bulk (60 and 70 °C) and suspension (70 °C) was studied, and in both polymerization systems, a good control of the molecular weight and polydispersity was observed. Stable suspension polymerizations were carried out over a range of CPDB concentrations, and with increasing CPDB concentration, the particle size and polydispersity index of the produced polymer decreased. The former was ascribed to the lower viscosities of the monomer and polymer droplets at low conversions, which caused easier breakup with the applied shear stresses. Lower polydispersity indices at higher CPDB concentrations were probably caused by a diminished gel effect, which was observed at lower CPDB concentrations at high conversions, causing a broadening of the molecular weight distribution. The livingness of the polymers formed in suspension was proven by successful chain extensions with methyl methacrylate, styrene, and 2‐hydroxyethyl methacrylate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2001–2012, 2005     

Trajectories of para- and freeomagnetic particles in HGMS filters with axial configurations

The trajectories of para-and ferromagnetic particles with velocities between 0.04 and 2.5 cm s⁻¹ have been investigated in an HGMS model system with axial configuration. A single-wire system has been observed by a TV system. The trajectories were compared with the ideal (inviscid flow) and laminar (viscous flow) model. The results agree with laminar flow model.     

Enantioselective silica-based monoliths modified with a novel aminosulfonic acid-derived strong cation exchanger for electrically driven and pressure-driven capillary chromatography

Silica monoliths modified with trans-(1S,2S)-2-(N-4-allyloxy-3,5-dichlorobenzoyl)amino cyclohexanesulfonic acid were tested for enantioselective separations of various chiral bases by aqueous and nonaqueous CEC as well as nano-HPLC. The optimization of the immobilization procedure showed that an intermediate selector (SO) coverage, as does result from a single static immobilization cycle in the capillary at 60 degrees C with an 8% (m/v) SO solution in methanol, affords maximal EOF and optimal enantioselectivity values, while a second immobilization cycle does not lead to any improvements. Furthermore, the mobile phase composition was examined regarding the effectiveness of aqueous phases (ACN/water and methanol/water) compared to nonaqueous eluents (ACN/methanol) in terms of separation selectivity and efficiency. Additionally, different acids of varying strengths were tested as co-ions in the ion-exchange process, including formic acid, acetic acid, methanesulfonic acid, and TFA (pK(a) from 4.75 to 0.5). It turned out that the effects regarding EOF and enantioselectivity were largely negligible. The chromatographic efficiencies of the new capillary columns were compelling and remarkable for bases. H-u curves established for mefloquine revealed a C-term contribution (resistance to mass transfer) by a factor of about six lower in CEC than in nano-HPLC and an A-term (flow maldistribution) about three times lower in the CEC mode. Theoretical plate heights as low as around 3-5 mum could be obtained in CEC over a wide flow range (0.5-1.5 mm/s). Run-to-run repeatabilities like in HPLC and excellent system stability promise the practical usefulness of the novel monolithic capillary column for enantiomeric composition analysis of pharmaceuticals by CEC.     

Characteristic negative ion fragmentations of deprotonated peptides containing post-translational modifications: mono-phosphorylated Ser, Thr and Tyr. A joint experimental and theoretical study

Peptides and proteins may contain post-translationally modified phosphorylated amino acid residues, in particular phosphorylated serine (pSer), threonine (pThr) and tyrosine (pTyr). Following earlier work by Lehmann et al., the [M-H]- anions of peptides containing pSer and pThr functionality show loss of the elements of H3PO4. This process, illustrated for Ser (and using a model system), is CH3CONH-C(CH2OPO3H2)CONHCH(3) --> [CH3CONHC(==CH2)CONHCH3 (-OPO3H2)] (a) --> [CH3CONHC(==CH2)CONHCH3-H]- + H3PO4, a process endothermic by 83 kJ mol(-1) at the MP2/6-31++G(d,p)//HF/6-31++G(d,p) level of theory. In addition, intermediate (a) may decompose to yield CH3CONHC(==CH2)CONHCH3 + H2PO4 - in a process exothermic by 3 kJ mol(-1). The barrier to the transition state for these two processes is 49 kJ mol(-1). Characteristic cleavages of pSer and pThr are more energetically favourable than the negative ion backbone cleavages of peptides described previously. In contrast, loss of HPO3 from [M-H]- is characteristic of pTyr. The cleavage [NH2CH(CH2-C6H4-OPO3H-)CO2H] --> [NH2C(CH2-C6H4-O-)CO2H (HPO3)] (b) --> NH2CH(CH2-C6H4-O-)CO2H + HPO3 is endothermic by 318 kJ mol(-1) at the HF/6-31+G(d)//AM1 level of theory. In addition, intermediate (b) also yields NH2CH(CH2-C6H4-OH)CO2H + PO3 - (reaction endothermic by 137 kJ mol(-1)). The two negative ion cleavages of pTyr have a barrier to the transition state of 198 kJ mol(-1) (at the HF/6-31+G(d)//AM1 level of theory) comparable with those already reported for negative ion backbone cleavages.     

Neutron activation analysis and X-ray Rayleigh and Raman scattering of hair and nail clippings as noninvasive bioindicators for Cu liver status in Labrador Retrievers

The heritability of chronic hepatitis in the Labrador Retriever is studied with the aim of identifying the related gene mutation. Identification of cases and controls is largely based on instrumental neutron activation analysis (INAA) Cu determination in liver biopsies. The burden for these companion animals may be reduced if nail clippings and hair (fur) could serve as a noninvasive indicator for the hepatic Cu concentrations. No correlation was found between hepatic Cu concentrations and Cu concentrations in hair and nail samples. However, hair and nail samples were also analyzed by X-ray tube excitation, taking advantage of the X-ray Compton, Rayleigh, and Raman scattering which reflects the organic components such as the type of melanin. Principal component analysis provided first indications that some differentiation between healthy and sick dogs could indeed be obtained from hair and nail analysis. Figure Principal component analysis of scattered region of x-ray fluorescence spectra of Labrador dog nails, demonstrating the differentiation towards dogs with high and low Cu liver levels (respectively positive and negative PC2 values) reflecting hepatitis, as well as gender (PC1: negative values for female and positive values for males)