Amperometric Biosensors for Tyramine Determination Based on Graphene Oxide and Polyvinylferrocene Modified Screen‐printed Electrodes

A comparison of the analytical characteristics of two tyramine biosensors, based on graphene oxide (GRO) and polyvinylferrocene (PVF) modified screen‐printed carbon electrodes (SPCE), is reported. Diamine oxidase (DAOx) or monoamine oxidase (MAOx) was immobilized onto the PVF/GRO modified SPCE to fabricate the biosensors. Surface characteristics and electrochemical behaviour of the modified SPCEs were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDX) and cyclic voltammetry (CV). Electrode surface composition and experimental variables such as pH and working potential were optimized in order to ensure a high performance. Under optimum experimental conditions, both DAOx/PVF/GRO/SPCE and MAOx/PVF/GRO/SPCE biosensors exhibited wide linear dynamic ranges for tyramine from 9.9×10^?7 to 1.2×10^?4 M and from 9.9×10^?7 to 1.1×10^?4 M, respectively. MAOx/PVF/GRO/SPCE biosensor showed higher sensitivity (11.98 μA mM^?1) for tyramine determination than the DAOx/PVF/GRO/SPCE biosensor (7.99 μA mM^?1). The substrate specifity of the biosensors to other biogenic amines namely histamine, putrescine, spermine, spermidine, tryptamine, β‐phenylethylamine and cadaverine was also investigated. The developed biosensors were successfully used for tyramine determination in cheese sample.     

Travelling wave solutions of generalized Klein–Gordon equations using Jacobi elliptic functions

Nonlinear Dynamics - This paper obtains exact travelling wave solutions of five various forms of the generalized nonlinear Klein–Gordon equations using Jacobi elliptic functions. Topological...     

Optimal control policies for ambulance diversion

Ambulance diversion (AD) is used by emergency departments (EDs) to relieve congestion by requesting ambulances to bypass the ED and transport patients to another facility. We study optimal AD control policies using a Markov Decision Process (MDP) formulation that minimizes the average time that patients wait beyond their recommended safety time threshold. The model assumes that patients can be treated in one of two treatment areas and that the distribution of the time to start treatment at the neighboring facility is known. Assuming Poisson arrivals and exponential times for the length of stay in the ED, we show that the optimal AD policy follows a threshold structure, and explore the behavior of optimal policies under different scenarios. We analyze the value of information on the time to start treatment in the neighboring hospital, and show that optimal policies depend strongly on the congestion experienced by the other facility. Simulation is used to compare the performance of the proposed MDP model to that of simple heuristics under more realistic assumptions. Results indicate that the MDP model performs significantly better than the tested heuristics under most cases. Finally, we discuss practical issues related to the implementation of the policies prescribed by the MDP.     

N,N'-disalicylidene-1,3-diaminopropane as a selective chelating titrant for copper(II)

This study was carried out to develop a new complexometric titration method for determination of copper. For this purpose, the standard solutions of copper(II) (10(-3)-10(-5) M) were potentiometrically titrated using N,N'-disalicylidene-1,3-diaminopropane (Schiff base) as titrant and copper(II)-selective electrode for end-point indication in both ammonium acetate and ammonia/ammonium chloride buffer media. The stoichiometry of titration reaction and interference effects of some metal ions on titration of copper were discussed. There was a good agreement between the results obtained by the proposed titration method and ethylenediaminetetraacetic acid (EDTA) titration method. The accuracy and precision of Schiff base method were tested by five replicate determinations both on the standard solution of copper(II) and standard reference materials. The results have indicated that the percentage of copper in alloys can be safely determined by using the Schiff base method without interference from many other metals in alloys.     

Theoretical study of structure, stability and infrared spectra of CH3X-SO3 (X = F, Cl, Br) complexes

Ab initio computational study of the electronic structure and infrared spectra of donor-acceptor complexes formed between SO3 and CH3X (X = F, Cl, Br) molecules was carried out at the MP2(full)/6-31G(d) level of theory. The calculated complexation energy at G2MP2 level shows that stability of complexes decrease, as CH3Cl-SO3 > CH3Br-SO3 > CH3F-SO3. The NBO partitioning scheme show that the lengthening of the C-F, C-Cl, and C-Br bond lengths, upon complexation, is due to an decreasing "s" character in these bonds.     

Liquid-membrane electrode sensitive to ammonia and aliphatic amines based on 1-[(2-oxyphenyl)iminomethly]-2-oxybenzene-O,O',N-ammin-nickel(II) complex

In this study, an ammonia-gas-sensing liquid-state membrane electrode based on 1-[(2-oxyphenyl)iminomethyl]-2-oxybenzene-O,O',N-ammin-nickel(II) (Ni(II)-Schiff base) as an ionophore was developed. This membrane electrode gave a very good performance and exhibited linear response with near-Nernstian slope of 50.7+/-0.5 mV per decade, within a concentration range of 1.0x10(-1)-1.0x10(-3) M. The electrode performance depends on the pH of the test solution and the optimum pH range was 10.0-11.5. The effect of concentration of internal solutions in the electrode was also investigated. The selectivity properties of the electrode towards aliphatic amines at a pH value of 10.2 were investigated with the mixed-solution method. Furthermore, the response time and lifetime of the electrode prepared were determined.     

Determination of platinum, palladium and rhodium in Pt-catalysts by high performance thin layer chromatography using densitometry

The determination of palladium and platinum in alumina-supported bimetallic Pt-Re, Pd and Pt catalysts at the 0.03 and 0.3% (m/m) levels, respectively, and of rhodium and platinum in platinum sieve catalysts at the 0.04% (m/m) level and in the 4.75–19.75% (m/m) range, respectively, is described. The platinum group metals in fresh or spent catalysts are determined chromatographically using densitometry by forming theirN,N-diethyl-N-benzoylthiourea complexes. The precision of the method, %RSD, is 0.4–3.5, 2.2–6.7, and 4.2–6.0 for Pt, Pd and Rh, respectively. The accuracy was tested using alumina-based and active carbon platinum and palladium standards. The results were also compared with those obtained by FAAS. There was at most 8% difference between the results obtained with these methods, except for one active carbon based Pd standard.     

Reactions of Enone Ethylene Ketals with Methyl Diazomalonate/Bis(acetylacetonato)copper(II)

Several cyclic and acyclic enones and their ethylene ketals/acetals were reacted with dimethyl diazomalonate under bis(acetylacetonato)copper(II) catalysis. Cyclohex-2-en-1-one ( 1 ) yielded only C–H insertion products 2 and 3 , whereas but-3-en-2-one gave a cyclopropane albeit in very low yield. The ethylene ketals 6 of cyclopent-2-en-1-one and cyclohex-2-en-1-one gave the corresponding cyclopropanes 7 , which were in turn cleaved to the ketones 8 . The acetals 9 and 10 of crotonaldehyde ((E)-but-2-enal) and cinnamaldehyde ((E)-3-phenylprop-2-enal), respectively, yielded C–O insertion and [2,3]-sigmatropic rearrangement products 11b, c and 12b, c , as well as cyclopropanes 11a and 11b , all of which are polyfunctional and synthetically useful compounds.     

Parametrization, molecular dynamics simulation, and calculation of electron spin resonance spectra of a nitroxide spin label on a polyalanine alpha-helix

The nitroxide spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-methyl-methanethiosulfonate (MTSSL), commonly used in site-directed spin labeling of proteins, is studied with molecular dynamics (MD) simulations. After developing force field parameters for the nitroxide moiety and the spin label linker, we simulate MTSSL attached to a polyalanine alpha-helix in explicit solvent to elucidate the factors affecting its conformational dynamics. Electron spin resonance spectra at 9 and 250 GHz are simulated in the time domain using the MD trajectories and including global rotational diffusion appropriate for the tumbling of T4 Lysozyme in solution. Analysis of the MD simulations reveals the presence of significant hydrophobic interactions of the spin label with the alanine side chains.