Magnetoresistance of Fe3O4/Au/Fe3O4 and Fe3O4/Au/Fe spin-valve structures

A detailed study of the in-plane magnetotransport properties of spin valves with one and two Fe₃O₄ electrodes is presented. Fe₃O₄/Au/Fe₃O₄ spin valves exhibit a clear anisotropic magnetoresistance in small magnetic fields but no giant magnetoresistance (GMR). The absence of GMR in these structures is due to simultaneous magnetization reversal in the two Fe₃O₄ layers. By contrast, a negative GMR effect is measured on Fe₃O₄/Au/Fe spin valves. The negative GMR is attributed to an electron spin scattering asymmetry at the Fe₃O₄/Au interface or an induced spin scattering asymmetry in the Au interfacial layers.     

Single electron transfer events and dynamical heterogeneity in the small protein azurin from Pseudomonas aeruginosa

Monitoring the fluorescence of single-dye-labeled azurin molecules, we observed the reaction of azurin with hexacyanoferrate under controlled redox potential yielding data on the timing of individual (forward and backward) electron transfer (ET) events. Change-point analysis of the time traces demonstrates significant fluctuations of ET rates and of mid-point potential E₀. These fluctuations are a signature of dynamical heterogeneity, here observed on a 14 kDa protein, the smallest to date. By correlating changes in forward and backward reaction rates we found that 6% of the observed change events could be explained by a change in midpoint potential, while for 25% a change of the donor–acceptor coupling could explain the data. The remaining 69% are driven by variations in complex association constants or structural changes that cause forward and back ET rates to vary independently. Thus, the observed spread in individual ET rates could be related in a unique way to variations in molecular parameters. The relevance for the understanding of metabolic processes is briefly discussed.

Observing electron transfer events in individual azurin molecules, we relate the spread in transfer rates in a unique way to variations in molecular parameters.     

Comparative study of recent wide-pore materials of different stationary phase morphology, applied for the reversed-phase analysis of recombinant monoclonal antibodies

Various recent wide-pore reversed-phase stationary phases were studied for the analysis of intact monoclonal antibodies (mAbs) of 150 kDa and their fragments possessing sizes between 25 and 50 kDa. Different types of column technology were evaluated, namely, a prototype silica-based inorganic monolith containing mesopores of ～250 Å and macropores of ～?1.1 μm, a column packed with 3.6 μm wide-pore core-shell particles possessing a wide pore size distribution with an average around 200 Å and a column packed with fully porous 1.7 μm particles having pore size of ～300 Å. The performance of these wide-pore materials was compared with that of a poly(styrene–divinyl benzene) organic monolithic column, with a macropore size of approximately 1 μm but without mesopores (stagnant pores). A systematic investigation was carried out using model IgG1 and IgG2 mAbs, namely rituximab, panitumumab, and bevacizumab. Firstly, the recoveries of intact and reduced mAbs were compared on the two monolithic phases, and it appeared that adsorption was less pronounced on the organic monolith, probably due to the difference in chemistry (C18 versus phenyl) and the absence of mesopores (stagnant zones). Secondly, the kinetic performance was investigated in gradient elution mode for all columns. For this purpose, peak capacities per meter as well as peak capacities per time unit and per pressure unit (PPT) were calculated at various flow rates, to compare performance of columns with different dimensions. In terms of peak capacity per meter, the core-shell 3.6 μm and fully porous 1.7 μm columns outperformed the two monolithic phases, at a temperature of 60 °C. However, when considering the PPT values, the core-shell 3.6 μm column remained the best phase while the prototype silica-based monoliths became very interesting, mostly due to a very high permeability compared with the organic monolith. Therefore, these core-shell and silica-based monolith provided the fastest achievable separation. Finally, at the maximal working temperature of each column, the core-shell 3.6 μm column was far better than the other one, because it is the only one stable up to 90 °C. Lastly, the loading capacity was also measured on these four different phases. It appeared that the organic monolith was the less interesting and rapidly overloaded, due to the absence of mesopores. On the other hand, the loading capacity of prototype silica-based monolith was indeed reasonable.     

Characteristics of distortion product otoacoustic emissions in the frog from L1,L2 maps

For a given set of stimulus frequencies (f1 ,f2), the level of distortion product otoacoustic emissions (DPOAEs) varies with the levels of the stimulus tones. By variation of the stimulus levels, L1,L2-maps for DPOAEs can be constructed. Here, we report on L1 ,L2-maps for DPOAEs from the frog ear. In general, these maps were similar to those obtained from the mammalian cochlea. We found a conspicuous difference between the equal-level contour lines for low-level and high-level DPOAEs, which could be modeled by a saturating and an expansive nonlinearity, respectively. The transition from the high-level to the low-level response was accompanied by a DPOAE phase-change, which increased from 0 to pi rad with increasing frequency. These results suggest that in the frog low-level and high-level DPOAEs are generated by separate nonlinear mechanisms. Also, there was a conspicuous difference in the growth of the low-level emissions from the two anuran auditory papillae. In the basilar papilla, this growth was expansive for the lowest stimulus levels and saturated for intermediate levels. This is consistent with the behavior of a Boltzman nonlinearity. In the amphibian papilla this growth was compressive, suggesting the additional effect of a compressive amplification mechanism on the generation of DPOAEs.     

Distortion product otoacoustic emissions provide clues hearing mechanisms in the frog ear

2f1-f2 and 2 f2-f1 distortion product otoacoustic emissions (DPOAEs) were recorded from both ears of male and female Rana pipiens pipiens and Rana catesbeiana. The input-output (I/O) curves obtained from the amphibian papilla (AP) of both frog species are analogous to I/O curves recorded from mammals suggesting that, similarly to the mammalian cochlea, there may be an amplification process present in the frog AP. DPOAE level dependence on L1-L2 is different from that in mammals and consistent with intermodulation distortion expectations. Therefore, if a mechanical structure in the frog inner ear is functioning analogously to the mammalian basilar membrane, it must be more broadly tuned. DPOAE audiograms were obtained for primary frequencies spanning the animals' hearing range and selected stimulus levels. The results confirm that DPOAEs are produced in both papillae, with R. catesbeiana producing stronger emissions than R. p. pipiens. Consistent with previously reported sexual dimorphism in the mammalian and anuran auditory systems, females of both species produce stronger emissions than males. Moreover, it appears that 2 f1-f2 in the frog is generated primarily at the DPOAE frequency place, while 2 f2-f1 is generated primarily at a frequency place around the primaries. Regardless of generation place, both emissions within the AP may be subject to the same filtering mechanism, possibly the tectorial membrane.     

Structural and magnetic properties of pulsed laser deposited SrRuO3/CoFe2O4/La2/3Sr1/3MnO3 magnetic oxide heterostructures on SrTiO3(001) and MgO(001)

We report on the growth of all-oxide SrRuO₃/CoFe₂O₄/La_2/3Sr_1/3MnO₃ and La_2/3Sr_1/3MnO₃/CoFe₂O₄/SrRuO₃ heterostuctures on SrTiO₃(001) and MgO(001) substrates by pulsed laser deposition. Structural analyses by X-ray diffraction and transmission electron microscopy clearly indicate the preservation of epitaxial relations when the La_2/3Sr_1/3MnO₃ layer is grown first, whereas trilayers with SrRuO₃ at the bottom are more disordered. Both the substrate material and the deposition sequence strongly influence the formation of various structural defects such as interfacial dislocations and sub-grain structures, and this is clearly reflected by a reduction of the saturation magnetization in the top electrode. When the substrate material and the deposition sequence are correctly chosen, however, the magnetic moments of the La_2/3Sr_1/3MnO₃ and SrRuO₃ layers reverse independently, and the La_2/3Sr_1/3MnO₃ layer retains bulk-like magnetic properties.     

Parameters affecting the separation of intact proteins in gradient-elution reversed-phase chromatography using poly(styrene-co-divinylbenzene) monolithic capillary columns

An experimental study was performed to investigate the effects of column parameters and gradient conditions on the separation of intact proteins using styrene-based monolithic columns. The effect of flow rate on peak width was investigated at constant gradient steepness by normalizing the gradient time for the column hold-up time. When operating the column at a temperature of 60 °C a small C-term effect was observed in a flow rate range of 1–4 μL/min. However, the C-term effect on peak width is not as strong as the decrease in peak width due to increasing flow rate. The peak capacity increased according to the square root of the column length. Decreasing the macropore size of the polymer monolith while maintaining the column length constant, resulted in an increase in peak capacity. A trade-off between peak capacity and total analysis time was made for 50, 100, and 250 mm long monolithic columns and a microparticulate column packed with 5 μm porous silica particles while operating at a flow rate of 2 μL/min. The peak capacity per unit time of the 50 mm long monolithic column with small pore size was superior when the total analysis time is below 120 min, yielding a maximum peak capacity of 380. For more demanding separations the 250 mm long monolith provided the highest peak capacity in the shortest possible time frame.     

Transferring Ions from Solution to the Gas Phase: The Two Basic Principles

The efficient formation of gaseous ions is the crucial step in all successful mass spectrometric experiments. The invention of electrospray ionization (ESI) has strongly facilitated this step by transferring preformed ions directly from solution to the gas phase – thereby circumventing the need to first convert analytes to the gas phase and then ionize them – and therefore ESI has become an extremely useful and widely applied MS technique. The invention of sonic spray ionization (SSI) has also allowed for the transfer of ions from solution into the gas phase, but without the assistance of a voltage or heating. Numerous ionization techniques, using similar principles to those applied in either ESI or SSI, have subsequently been developed. Although experimental conditions used in such techniques vary markedly, herein we argue that they are all based on either one of two basic principles by which ions can be transferred from solution to the gas phase, that is: via (1) neutralizing the counter ion, or (2) separating the ions. We have selected 35 such techniques and categorized them accordingly. This article thereby aims to establish the basic principles by which gaseous ions can be obtained from solvated ions. We further propose that any new ionization technique used to transfer solvated ions to the gas phase will similarly fall into one of these two mechanistic categories.

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