CEMS of Sb+ implanted stainless steels

Martensitic transformations have been analysed in a series of antimony implanted austenitic stainless steels using CEMS. The implanted samples contain about 70 vols martensite, which is considerably more than can be formed conventionally by plastic deformation or cooling below the martensite start temperature. CEM spectra from implantation induced martensite and from martensite formed in conventional processes are virtually identical. In both cases the hyperfine field is ≈ 25T.     

Analytical and numerical study on grating depth effects in grating coupled waveguide sensors

The in-coupling process for grating-coupled planar optical waveguide sensors is investigated in the case of TE waves. A simple analytical model based on the Rayleigh–Fourier–Kiselev method is applied to take into account the depth of the grating coupler, which is usually neglected in the modeling. Analytical expressions are derived both for the position and width of the in-coupling peaks to illustrate the effects of grating depth on the guided mode resonances in grating coupled waveguide sensors. Numerical computations verify the model for shallow gratings both in terms of peak shape and position and provide the limitations for the analytical formulas.     

High-performance size-exclusion chromatographic procedure for the determination of fluoresceinyl isothiocyanate dextrans of various molecular masses in biological media

A high-performance size-exclusion chromatographic procedure, using Nucleosil Diol, for the quantitative analysis of fluoresceinyl isothiocyanate dextrans of various molecular masses (10,000-150,000) in biological media was developed. The influence of the molecular mass and the degree of substitution of the conjugates on the chromatographic behaviour are discussed. In addition to quantitation, the molecular mass of the conjugates with degree of substitution below 1.6 could be estimated from the chromatograms. Linear standard calibration curves were obtained at concentrations down to 0.050 micrograms ml-1 in rabbit plasma and urine and homogenates of rabbit liver, lymph node and muscle when the derivative (degree of substitution 0.85) was monitored by fluorescence detection (lambda ex = 493 nm, lambda em = 520 mm). The fluoresceinyl isothiocyanate dextrans were found to be stable for more than three days at 37 degrees in all biological media under investigation. A pH-rate profile for the alkaline hydrolysis of fluoresceinyl isothiocyanate dextrans was constructed. The applicability of the method to pharmacokinetic studies was demonstrated by recording the plasma concentration-time profile of a fluoresceinyl isothiocyanate dextran T-70 conjugate following intravenous injection to a rabbit. In relation to future pharmacokinetic investigations on dextran conjugates, the results reported indicate that labelling of the parent dextran with fluoresceinyl isothiocyanate and monitoring of the fluoresceinyl isothiocyanate dextran conjugate throughout the organism using the described method is a promising development.     

Interaction between superconducting vortices and a Bloch wall in ferrite garnet films

A theoretical model for how Bloch walls occurring in in-plane magnetized ferrite garnet films can serve as efficient magnetic micromanipulators is presented. As an example, the walls' interaction with Abrikosov vortices in a superconductor in close contact with a garnet film is analyzed within the London approximation. The model explains how vortices are attracted to such walls, and excellent quantitative agreement is obtained for the resulting peaked flux profile determined experimentally in NbSe(2) using high-resolution magneto-optical imaging of vortices. In particular, this model, when generalized to include charged magnetic walls, explains the counterintuitive attraction observed between vortices and a Bloch wall of opposite polarity.     

Dramatic role of critical current anisotropy on flux avalanches in MgB2 films

Anisotropic penetration of magnetic flux in MgB(2) films grown on vicinal sapphire substrates is investigated using magneto-optical imaging. Regular penetration above 10 K proceeds more easily along the substrate surface steps, the anisotropy of the critical current being 6%. At lower temperatures the penetration occurs via abrupt dendritic avalanches that preferentially propagate perpendicular to the surface steps. This inverse anisotropy in the penetration pattern becomes dramatic very close to 10 K where all flux avalanches propagate in the strongest pinning direction. The observed behavior is fully explained using a thermomagnetic model of the dendritic instability.     

Potential of prodendronic polyamines with modulated segmental charge density as novel coating for fast and efficient analysis of peptides and basic proteins by CE and CE‐MS

In this work, the suitability of a new polymer family has been investigated as capillary coatings for the analysis of peptides and basic proteins by CE. This polymer family has been designed to minimize or completely prevent protein–capillary wall interactions and to modify the EOF. These coating materials are linear polymeric chains bearing as side cationizable moiety a dentronic triamine derived from N,N,N’,N’‐tetraethyldiethylenetriamine (TEDETA), which is linked to the backbone through a spacer (unit labeled as TEDETAMA). Four different polymers have been prepared and evaluated: a homopolymer which comprised only of those cationizable repetitive units of TEDETAMA, and three copolymers that randomly incorporate TEDETAMA together with neutral hydrosoluble units of N‐(2‐hydroxypropyl) methacrylamide (HPMA) at different molar percentages (25:75, 50:50 and 75:25). It has been demonstrated that the composition of the copolymers influences the EOF and therefore the separation of the investigated biopolymers. Among the novel polymers studied, poly‐(TEDETAMA‐co‐HPMA) 50:50 copolymer was successfully applied as coating material of the inner capillary surface in CE‐UV and CE‐MS, providing EOF reversing together with fast and efficient baseline separation of peptides and basic proteins. Finally, the feasibility of the polymer‐coated capillary was shown through the analysis of lysozyme in a cheese sample.     

Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium‐Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates

The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium‐catalyzed aminocarbonylation reaction of the corresponding α‐fluoroalkyl o‐iodobenzylamines. A base‐mediated anti β‐hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine‐tuning the pK_a of the base.     

Analysis of chiral amino acids in cerebrospinal fluid samples linked to different stages of Alzheimer disease

Chiral micellar electrokinetic chromatography with laser-induced fluorescence detection (chiral-MEKC-LIF) was used to investigate D- and L-amino acid contents in cerebrospinal fluid (CSF) samples related to different Alzheimer disease (AD) stages. CSF samples were taken from (i) control subjects (S1 pool), (ii) subjects showing a mild cognitive impairment who remained stable (S2 pool), (iii) subjects showing an mild cognitive impairment that progressed to AD (S3 pool) and (iv) subjects diagnosed with AD (S4 pool). The optimized procedure only needed 10 μL of CSF and it included sample cleaning, derivatization with FITC and chiral-MEKC-LIF separation. Eighteen standard amino acids were baseline separated with efficiencies up to 703,000 plates/m, high sensitivity (LODs in the nM range) and good resolution (values ranging from 2.6 to 9.5). Using this method, L-Arg, L-Leu, L-Gln, γ-aminobutyric acid, L-Ser, D-Ser, L-Ala, Gly, L-Lys, L-Glu and L-Asp were detected in all the CSF samples. S3 and S4 samples (i.e. AD subjects) showed significant lower amounts of L-Arg L-Lys, L-Glu and L-Asp compared to the non-AD S1 and S2 samples, showing in the S4 group the lowest amounts of L-Arg L-Lys, L-Glu and L-Asp. Moreover, γ-aminobutyric acid was significantly higher in AD subjects with the highest amount also found for S4. No significant differences were observed for the rest of amino acids including D-Ser. Based on the obtained chiral-MEKC-LIF data, it was possible to correctly classify all the samples into the four groups. These results demonstrate that the use of enantioselective procedures as the one developed in this work can provide some new light on the investigations of AD, including the discovery of new biomarkers related to different stages of AD.