Comparison of CID, ETD and metastable atom-activated dissociation (MAD) of doubly and triply charged phosphorylated tau peptides

The fragmentation behavior of the 2+ and 3+ charge states of eleven different phosphorylated tau peptides was studied using collision-induced dissociation (CID), electron transfer dissociation (ETD) and metastable atom-activated dissociation (MAD). The synthetic peptides studied contain up to two known phosphorylation sites on serine or threonine residues, at least two basic residues, and between four and eight potential sites of phosphorylation. CID produced mainly b-/y-type ions with abundant neutral losses of the phosphorylation modification. ETD produced c-/z-type ions in highest abundance but also showed numerous y-type ions at a frequency about 50% that of the z-type ions. The major peaks observed in the ETD spectra correspond to the charge-reduced product ions and small neutral losses from the charge-reduced peaks. ETD of the 2+ charge state of each peptide generally produced fewer backbone cleavages than the 3+ charge state, consistent with previous reports. Regardless of charge state, MAD achieved more extensive backbone cleavage than CID or ETD, while retaining the modification(s) in most cases. In all but one case, unambiguous modification site determination was achieved with MAD. MAD produced 15-20% better sequence coverage than CID and ETD for both the 2+ and 3+ charge states and very different fragmentation products indicating that the mechanism of fragmentation in MAD is unique and complementary to CID and ETD.     

Estimation of free copper ion concentrations in blood serum using T(1) relaxation rates

The water proton relaxation rate constant R(1)=1/T(1) (at 60 MHz) of blood serum is substantially increased by the presence of free Cu2+ ions at concentrations above normal physiological levels. Addition of chelating agents to serum containing paramagnetic Cu2+ nulls this effect. This was demonstrated by looking at the effect of adding a chelating agent-D-penicillamine (D-PEN) to CuSO4 and CuCl2 aqueous solutions as well as to rabbit blood serum. We propose that the measurement of water proton spin-lattice relaxation rate constants before and after chelation may be used as an alternative approach for monitoring the presence of free copper ions in blood serum. This method may be used in the diagnosis of some diseases (leukaemia, liver diseases and particularly Wilson's disease) because, in contrast to conventional methods like spectrophotometry which records the total number of both bound and free ions, the proton relaxation technique is sensitive solely to free paramagnetic ions dissolved in blood serum. The change in R(1) upon chelation was found to be less than 0.06 s(-1) for serum from healthy subjects but greater than 0.06 s(-1) for serum from untreated Wilson's patients.     

Cytoplasmic RNA and nuclear changes detected cytochemically during the degeneration of salivary glands of the tick Rhipicephalus sanguineus (Latreille, 1806) (Acari, Ixodidae)

The present study reports cytochemistry data about salivary glands of females (unfed, engorged, and at day three post-engorgement) and males (unfed, at day seven post-attachment, and at days three and seven post-detachment from the host) of the tick Rhipicephalus sanguineus. The results revealed nuclear changes in engorged females and at day three post-engorgement, and in males in all stages (except unfed). These changes were more prominent in females. Cytoplasmic changes were also observed in cells of all acini of males and females. In types II and III acini of engorged females, nuclear changes were observed in the shape (irregular, with blebs, fragmenting or fragmented), size (enlarged or reduced), and arrangement and condensation level of chromatin (marginal or as blebs). Changes were also detected in nucleoli, regarding their shape (fragmenting or fragmented), size (enlarged), and location (central, marginal or as blebs). Some nucleoli were also compacted or disorganized. In females at day three pos-engorgement, all acini exhibited similar changes to those observed in engorged females. RNA staining was stronger in cells of engorged females than those at day three post-engorgement. In males at day seven post-attachment, cells of types II, III, IV acini presented changes in the size of the nucleus and condensation level of chromatin similar to those of females. The shape of the nucleus was round, irregular or undergoing fragmentation, and the chromatin was located at the margin or throughout the nucleus. The changes in the nucleolus were similar to those of females, regarding size and organization, although round-shaped and in the central location. In males at day three post-detachment, cells of all acini exhibited nuclear changes similar to those of males at day seven post-attachment, in addition to the fragmentation of the nucleolus. At day seven post-detachment, changes were detected in all acini similar to the observed in males at day seven post-attachment. Regarding cytoplasmic RNA, staining was prominent in males at day seven post-attachment and weak in those at day seven post-detachment from the host. In females as well as males, different RNA staining patterns in the cytoplasm and nuclear changes characterized apoptotic cell death.     

Magnetic characterization of some nanometric iron oxides

Nanosized magnetite particles embedded in polypyrrole matrix have been studied by Mössbauer and electron magnetic resonance spectroscopy. Comparison with as grown magnetite is made. Hyperfine fields distribution is determined and line shape of resonance curves are discussed in terms of composite structure, sizes and treatments.     

Slope detection method by modulated speckle patterns

An optical technique for slope detection by using as storing medium a photorefractive BSO crystal is proposed. The technique relays in that a local tilt produced in a diffusing reflective surface can be mapped as a speckle transversal shifting in a plane perpendicular to the optical axis. The volume nature of the storing medium is quite adequate to highlight the speckle volume nature and its associated properties. Experimental results obtained by using a rubber vibrating membrane are presented.     

Synthesis and characterization of PMMA/silylated MMTs

Commercially available Sodium clay (Dellite HPS) and organo-clay (Dellite 72T) are modified via a silylation reaction. These silylated clays are characterized by IR, XRD, thermogravimetric analyses, and their equilibrium contact angles are measured. They are used to prepare nanocomposites at different loading percentage (1, 3, 5% wt) by in situ intercalative polymerization of Methyl methacrylate and morphology and thermal properties of nanocomposites are examined. SEM images of nanocomposites fractured surface show the absence of clays aggregates, confirming a good dispersion and distribution of montmorillonites in the polymer matrix. The effects of modified clays on the thermal properties of nanocomposites are analyzed by differential scanning calorimetry and thermogravimetric analyses showing an increase of glass and decomposition temperatures of all nanocomposites respect to homopolymer ones. The best results are obtained in the presence of silylated montmorillonites, clearly the organosilane improves the compatibility between polymer matrix and clay and as effect the properties of nanocomposites.     

Ferroelectric switching behavior of pulsed laser deposited Ba0.8Sr0.2TiO3 thin films

The effect of pulse amplitude on the ferroelectric and switching properties of pulsed laser deposited Ba_0.8Sr_0.2TiO₃ thin films has been studied. The structural and morphological analysis revealed that the films had a well crystallized perovskite phase and grain size of about 30–40 nm. A well saturated P–E hysteresis loop was observed with a remnant polarization (P_r) ≈ 4.8 μC/cm² and a coercive field ≈ 100 kV/cm at a frequency of 1 kHz. The P_r has been found to be decreased only 4.3% after passing 8.0 × 10⁸ cycles. The analysis of switching response with nucleation limited switching model reveals that characteristic switching time (t₀) variance is due to the random distribution of the local electric fields. The peak value of polarization current and t₀ exhibits exponential dependence on reciprocal of pulse amplitude.     

Electrosprayed NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles for long cycle life and high-power Li-ion battery anode

Electrospraying-based synthesis of NiCo₂O₄ (NCO-ES) nanoparticles that exhibit long cycle life and high rate capability is reported. The results are compared with a conventionally prepared NiCo₂O₄ sample by direct annealing (NCO-DA). The structure and morphology of NCO-ES and NCO-DA nanoparticles have been characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy to confirm the size, morphology, structure, and surface chemistry of the as-prepared samples. Electrochemical testing established that the NCO-ES sample displayed enhanced Li-ion storage performance. The NCO-ES delivered a discharge capacity of almost 370 mAh/g at the end of 50 cycles at 1C rate (890 mA/g) while only 180 mAh/g was retained for the NCO-DA sample at the same condition. At a high rate of 5C (4450 mA/g), NCO-ES electrodes delivered a stabilized specific capacity of 225 mAh/g with almost 100% Coulombic efficiency over 1000 cycles. Its rate capability and cycle life were found to be superior to NCO-DA electrodes. The nanoscale grain boundaries in the NCO-ES sample enhanced the lithium-ion diffusion and enabled high rate capability. The impedance analysis at different stages of lithiation/delithiation indicates a lower impedance and better kinetics as one of the reasons for better performance of the NCO-ES sample.     

Disappearance of criticality in thermal ignition for a simple reactive viscous flow

Conditions for the disappearance of criticality for reactive plane-Poiseuille flow are obtained by means of a perturbation series in the viscous heating parameter; an approximation to the Arrhenius reaction-rate term proposed in this journal by Bazley and Wake is used.

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Résumé On cherche les conditions pour la disparition de la limite critique pour l'écoulement Poiseuille de réactif entre deux plans en utilisant une série de perturbation de termes d'un paramètre que représente les effets thermiques de la viscosité; nous employons une approximation proposée dans ce journal par Bazley et Wake qui simplifie le terme d'Arrhenius dans l'équation de la balance de chaleur.