Amine oxidase amperometric biosensor coupled to liquid chromatography for biogenic amines determination

A selective and sensitive method is presented for biogenic amines (BA) determination. The novelty consists in coupling a highly selective electrochemical biosensor to a weak acid cation-exchange column for online detection of amines. A bienzyme design, based on a recently isolated amine oxidase from grass pea and commercial horseradish peroxidase, was used for the biosensor construction. The enzymes were co-immobilized on the surface of a graphite electrode together with the electrochemical mediator (Os-redox polymer). The electrochemical detection was performed at a low applied potential (?50 mV vs. Ag/AgCl, KCl_0.1 M), where biases from interferences are minimal. The separation and determination of six BA, with relevance in food analysis (tyramine, putrescine, cadaverine, histamine, agmatine and spermidine), were investigated. Irrespective of the BA nature, the amine oxidase-based biosensor showed a linear response up to 5 mM, and its sensitivity decreases in the following order: cadaverine, putrescine, spermidine, agmatine, histamine and tyramine. The approach was used to estimate the BA content in fish samples, after their extraction with methanesulfonic acid.     

A 2D coordination polymer with canted ferromagnetism constructed from ferromagnetic [Ni(II)Co(II)] nodes

A bimetallic coordination polymer, infinity (2)[{LNi (II)Co (II)}(dca) 2], has been constructed from heterobinuclear [Ni (II)Co (II)] nodes and dicyanamido spacers [L (2-) is the dianion of the Schiff base resulting from the 2:1 condensation of 3-methoxysalicyladehyde with 1,3-propanediamine; L (2-) = N, N'-propylenebis(3-methoxysalycilideneiminato)]. The intranode Co (II)-Ni (II) interaction was found to be ferromagnetic because of the orthogonality of the magnetic orbitals. Below 12 K, the onset of the canted ferromagnetic ordering is observed.     

Quantum Gravity from the Point of View of Locally Covariant Quantum Field Theory

We construct perturbative quantum gravity in a generally covariant way. In particular our construction is background independent. It is based on the locally covariant approach to quantum field theory and the renormalized Batalin–Vilkovisky formalism. We do not touch the problem of nonrenormalizability and interpret the theory as an effective theory at large length scales.     

Amplification phenomena of Casimir force fluctuations on close scatterers coupled via a coherent fermionic fluid

We study the mechanical actions affecting close scatterers immersed in a coherent fermionic fluid. Using a scattering field theory, we theoretically analyse the single-scatterer and the two-scatterer case. Concerning the single-scatterer case, we find that a net force affects the scatterer dynamics only in non-equilibrium condition, i.e. imposing the presence of a non-vanishing particle current flowing through the system. The force fluctuation (variance) is instead not negligible both in equilibrium and in non-equilibrium conditions. Concerning the two-scatterer case, an attractive fluid-mediated Casimir force is experienced by the scatterers at small spatial separation, while a decaying attractive/repulsive behavior as a function of the scatterer separation is found. Furthermore, the Casimir force fluctuations acting on a given scatterer in close vicinity of the other present an oscillating behavior reaching a long distance limit comparable to the noise level of the single-scatterer case. The relevance of these findings is discussed in connection with fluctuation phenomena in low-dimensional nanostructures and cold atoms systems.     

Detection of negative molecular ions in acrylic acid plasma: some implications for polymerization mechanisms

There is much scientific and commercial interest in plasma polymers to modify surface chemistry. To date, only neutral and positively charged species have been detected in the commonly applied acrylic acid plasma. Using time-averaged negative ion mass spectrometry, we demonstrate that large, negatively charged species exist in the plasma, contrary to previous studies that detected only neutral and positive species. We briefly outline how negative molecules may contribute to the deposition of plasma polymer in the acrylic acid system.     

Finite element approximation of spatially extended predator–prey interactions with the Holling type II functional response

We study the numerical approximation of the solutions of a class of nonlinear reaction–diffusion systems modelling predator–prey interactions, where the local growth of prey is logistic and the predator displays the Holling type II functional response. The fully discrete scheme results from a finite element discretisation in space (with lumped mass) and a semi-implicit discretisation in time. We establish a priori estimates and error bounds for the semi discrete and fully discrete finite element approximations. Numerical results illustrating the theoretical results and spatiotemporal phenomena are presented in one and two space dimensions. The class of problems studied in this paper are real experimental systems where the parameters are associated with real kinetics, expressed in nondimensional form. The theoretical techniques were adapted from a previous study of an idealised reaction–diffusion system (Garvie and Blowey in Eur J Appl Math 16(5):621–646, 2005).     

Synthesis of a new series of pyrazolo[1,5‐a]pyrimidines structurally related to zaleplon

The reaction between 3‐(dimethylamino)/3,3‐bis(methylthio)‐1‐(substituted)prop‐2‐en‐1‐ones and 4‐substituted‐5‐amino‐1H‐pyrazoles afforded new pyrazole[1,5‐a]pyrimidines structurally related to Zaleplon. The chemical modifications introduced at the 3‐, 5‐, and 7‐positions of the bicyclic structure revealed new promising candidates for the treatment of sleep disorders.     

Pulsed and continuous wave acrylic acid radio frequency plasma deposits: plasma and surface chemistry

Plasma polymers have been formed from acrylic acid using a pulsed power source. An on-pulse duration of 100 micros was used with a range of discharge off-times between 0 (continuous wave) and 20,000 micros. X-ray photoelectron spectroscopy (XPS) has been used in combination with trifluoroethanol (TFE) derivatization to quantify the surface concentration of the carboxylic acid functionality in the deposit. Retention of this functionality from the monomer varied from 2% to 65%. When input power was expressed as the time-averaged energy per monomer molecule, E(mean), the deposit chemistry achieved could be described using a single relationship for all deposition conditions. Deposition rates were monitored using a quartz crystal microbalance, which revealed a range from 20 to 200 microg m(-2) s(-1), and these fell as COOH functional retention increased. The flow rate was found to be the major determinant of the deposition rate, rather than being uniquely defined by E(mean), connected to the rate at which fresh monomer enters the system in the monomer deficient regime. The neutral species were collected in a time-averaged manner. As the energy delivered per molecule in the system (E(mean)) decreased, the amount of intact monomer increased, with the average neutral mass approaching 72 amu as E(mean) tends to zero. No neutral oligomeric species were detected. Langmuir probes have been used to determine the temporal evolution of the density and temperature of the electrons in the plasma and the plasma potential adjacent to the depositing film. It has been found that even 500 micros into the afterglow period that ionic densities are still significant, 5-10% of the on-time density, and that ion accelerating sheath potentials fall from 40 V in the on-time to a few volts in the off-time. We have made the first detailed, time- and energy-resolved mass spectrometry measurements in depositing acrylic acid plasma. These have allowed us to identify and quantify the positive ion species in the acrylic acid plasma during both the on- and the off- periods. The relative intensities of oligomeric species of the type [nM + H]+ as large as n = 3 were observed to increase in the off-time suggesting vapor phase polymerization after power input to the plasma was ceased. The energy distribution functions of these ions demonstrated that they were produced in the plasma in both the on- and the off-times. This remarkable observation contradicts the assumptions usually made when speculating on pulsed plasma that ions have very short lifetimes, although it is anticipated that radicals still have significantly longer lifetimes, estimated from calculation to be in excess of 1 ms. The increase in average positive ion mass during the off-period can be related to the lower mobility of the heavier components, reducing their relative loss to surfaces, and the polymer chain growth in the gas phase due to the ion-neutral collisions. The implications of these observations are discussed in light of polymerization mechanisms proposed from continuous acrylic acid and millisecond pulsing plasmas.     

Experimental evidence and consequences of rare events in quantum tunneling

Tiny spatial fluctuations of tunnel barrier parameters are shown to have dramatic consequences on the statistical properties of quantum tunneling. A direct experimental evidence is provided that the tunnel current through metal-oxide junctions, imaged at a nanometric scale, exhibits broad statistical distributions extending over more than 4 orders of magnitude. Striking effects of broad current distributions are shown: the total tunnel transmission is dominated by few highly transmitting sites and the typical current density varies strongly with the size of the junction. Moreover, self-averaging of the tunnel current fluctuations occurs only for unexpectedly large junction areas. Received 1 April 1999     

Ab initio and DFT Study on 2H-Isoxazol-5-one: Consequences of Strong Intermolecular Hydrogen-Bond Formation in Supramolecular Structures

Ab initio and density-functional-theory (DFT) calculations on 2H-isoxazol-5-one (A), its linear dimer (LD), cyclic dimer (CD), and cyclic trimer (CT), have been performed with several basis sets in the gas phase, including electron correlation by second-order Møller-Plesset perturbation theory. The calculated complexation energy for the intermolecular H-bonded trimer as well as the corresponding geometric changes are in good agreement with the notion of resonance-assisted intermolecular H-bond formation. Bond distances and angles of the optimized geometry of CT are in accordance with the X-ray-diffraction data found on a trimeric supramolecular complex of parent compound 4-(2-methoxybenzyl)-3-phenyl-4H-isoxazol-5-one. Ab initio and DFT geometry optimizations are also reproducing exactly the large asymmetry in bond angles around the CO group that is systematically present in all literature available X-ray data for analogous heterocyclic penta-atomic compounds.