Inter-particle spin-polarized tunneling in arrays of magnetite nanocrystals

Inter-particle spin-polarized tunneling was measured in an organically capped magnetite nanocrystal (NC) array deposited between 30 nm spaced gold electrodes. Magnetoresistance (MR) measurements performed around the blocking temperature (T_b) of the magnetic moments of the particles in the array, which was relatively high (220 K), yielded negative MR values of the order of 10-25% under moderate magnetic fields of several kOe. The field dependence of the MR followed closely the square of the film's magnetization and its voltage dependence indicated maximal spin polarization around the Fermi level. These findings suggested that the measured MR is the result of spin-polarized tunneling between individual magnetite NCs acting as superparamagnetic spin polarizers.     

The Asymptotic and Numerical Inversion of the Marcum Q‐Function

The generalized Marcum functions appear in problems of technical and scientific areas such as, for example, radar detection and communications. In mathematical statistics and probability theory these functions are called the noncentral gamma or the noncentral chi‐squared cumulative distribution functions. In this paper, we describe a new asymptotic method for inverting the generalized Marcum Q‐function and for the complementary Marcum P‐function. Also, we show how monotonicity and convexity properties of these functions can be used to find initial values for reliable Newton or secant methods to invert the function. We present details of numerical computations that show the reliability of the asymptotic approximations.     

Chaotic dynamic and control for micro-electro-mechanical systems of massive storage with harmonic base excitation

This paper explores chaotic behaviour and control of micro-electro-mechanical systems (MEMS), which consist of thousands of small read/write probe tips that access gigabytes of data stored in a non-volatile magnetic surface. The model of the system is formed by two masses connected by a nonlinear spring and a viscous damping. The paper shows that, by means of an adequate feedback law, the masses can behave as two coupled Duffing’s oscillators, which may reach chaotic behaviour when harmonic forces are applied. The chaotic motion is destroyed by applying the following control strategies: (i) static output feedback control law with constant forces and (ii) geometric nonlinear control. The aim is to drive the masses to a set point even with harmonic base excitation, by using chaotic dynamics and nonlinear control. The paper shows that it is possible to obtain a positioning time around a few ms with sub-nanometre accuracy, velocities, accelerations and forces, as it appears in the design of present MEMS devices. Numerical simulations are used to verify the mathematical discussions.     

Structural and Spectral Study of Nickel(II) Complexes of Pyridyl bis{3‐piperidyl‐, bis{hexamethyleneiminyl‐, bis{N(4)‐diethyl‐, and bis{N(4)‐dipropylthiosemicarbazones}

Pyridyl bis(N(4)‐substituted thiosemicarbazones), in which the substituents replacing the NH₂ group on the thiosemicarbazone moieties are piperidyl, H₂Plpip; hexamethyleneiminyl, H₂Plhexim; diethylamino, H₂Pl4DE; and dipropylamino, H₂Pl4DP, have been synthesized. These bis(thiosemicarbazones) and their nickel(II) complexes have been characterized with IR, electronic, mass, and ¹H and ¹³C NMR spectra. Crystal structures have been solved for H₂Plpip and all four nickel(II) complexes. H₂Plpip does not possess hydrogen bonding between the thiosemicarbazone moieties, but is in the Z isomeric form with intramolecular hydrogen bonding from both thiosemicarbazone moieties to pyridine nitrogen atoms. The nickel(II) complexes possess square‐planar N₂S₂ (i. e., imine nitrogen and thiolato sulfur atoms) centers and the two pyridine ring nitrogen atoms are not coordinated.     

Cloud point extraction for cobalt preconcentration with on-line phase separation in a knotted reactor followed by ETAAS determination in drinking waters

A novel method for cobalt preconcentration by cloud point extraction with on-line phase separation in a PTFE knotted reactor and further determination by electrothermal atomic absorption spectrometry (ETAAS) is proposed. The cloud point system was formed in the presence of non-ionic micelles of polyethyleneglycolmono-p-nonylphenylether (PONPE 7.5) and it was retained on the inner walls of a knotted reactor (KR). The surfactant rich-phase was removed from the knotted reactor with 75 microL of methanol acidified with 0.8 mol L(-1) nitric acid, directly into the dosing hole of the L'Vov graphite tube. An enrichment factor of 15 was obtained with a preconcentration time of 60 s, with respect to the direct determination of cobalt by ETAAS in aqueous solutions. The value of the detection limit for the preconcentration of 5 mL of sample solution was 10 ng L(-1). The precision, expressed as the relative standard deviation (R.S.D.), for 10 replicate determinations at 0.5 microg L(-1) Co level was 4.5%. Verification of the accuracy was carried out by analysis of a standard reference material (NIST SRM 1640e "Trace elements in natural water"). The method was successfully applied to the determination of cobalt in drinking water samples.     

Dicobalt hexacarbonyl complexes of alkynyl imines in a sequential Staudinger/Pauson-Khand process. A route to new fused tricyclic beta-lactams

Dicobalt hexacarbonyl complexes of alkynyl imines were allowed to react with ketenes via Staudinger reaction. Sequential [2 + 2] cycloaddition/Pauson-Khand reaction led to structurally new fused-tricyclic beta-lactams and fused-azabicyclic cyclopentenones. Chemoselectivity, scope, and limitation of the process were investigated.     

Solution structure of a peptide nucleic acid duplex from NMR data: features and limitations

This paper describes the results of a 1D and 2D NMR spectroscopy study of a palindromic 8-base pair PNA duplex GGCATGCC in H2O and H2O-D2O solutions. The (1)H NMR peaks have been assigned for most of the protons of the six central base pairs, as well as for several amide protons of the backbone. The resulting 36 interbase and base-backbone distance restraints were used together with Watson-Crick restraints to generate the PNA duplex structure in the course of 10 independent simulated annealing runs followed by restrained molecular dynamics (MD) simulations in explicit water. The resulting PNA structures correspond to a P-type helix with helical parameters close to those observed in the crystal structures of PNA. Based on the current limited number of restraints obtained from NMR spectra, alternative structures obtained by MD from starting PNA models based on DNA cannot be ruled out and are also discussed.     

Effect of the paste molding pressure on the mechanical strength of an iron oxide catalyst in the dehydrogenation of methylbutenes

The effect of the paste molding pressure on the physicomechanical and texture characteristics of catalysts was studied. An indirect criterion is suggested to evaluate the molding pressure in industrial extruders, whose optimal value ensures good physicomechanical properties of the catalysts and kinetic control over the catalyzed reaction. The results obtained were verified in paste molding on various industrial extruders, and this enabled the optimal choice of the molding equipment.     

Chemometric tools improving the determination of anti-inflammatory and antiepileptic drugs in river and wastewater by solid-phase microextraction and liquid chromatography diode array detection

An analytical method for the simultaneous determination of seven non-steroidal anti-inflammatory drugs (naproxen, ketoprofen, diclofenac, piroxicam, indomethacin, sulindac and diflunisal) and the anticonvulsant carbamazepine in river and wastewater is reported. The method involves pre-concentration and clean-up by solid-phase microextraction using polydimethylsiloxane/divinylbenzene fibers, followed by liquid chromatography with diode array detection analysis. Owing to the fact that river water samples did not contain interferences and no sensitivity changes due to sample matrix were observed, external calibration was implemented. Standardization was also applied in order to carry out the prediction step by preparing only two diluted standards that were subjected to the pre-concentration step and a set of standards prepared in solvent. For the analysis of wastewater samples, in contrast, it was necessary to implement standard addition calibration in combination with the multivariate curve resolution-alternating least squares (MCR-ALS) algorithm, which allowed us to overcome matrix effect and exploit the second order advantage. Recoveries ranging from 72% to 125% for all pharmaceuticals proved the accuracy of the proposed method in river water samples. On the other hand, wastewater sample recoveries ranged from 83% to 140% for all pharmaceuticals, showing an acceptable performance – considering this sample contains no modeled interferences.