Validation of a method for arsenic speciation in food by ion chromatography-inductively coupled plasma/mass spectrometry after ultrasonic-assisted enzymatic extraction

A fully validated and rapid quantitative method is presented for determination of inorganic arsenic [arsenite, As(III) and arsenate, As(V)] and organic arsenic species (methylarsonic acid, dimethylarsinic acid, and arsenobetaine) by ion chromatography paired with inductively coupled plasma/MS after ultrasonic-assisted enzymatic extraction (UAEE) in rice- and seafood-based raw materials and finished products. This method gives toxicological meaning to arsenic analysis, since the sum of the toxic chemical forms As(III) and As(V) can be determined. In contrast to classical water-methanol extraction, UAEE enables drastic acceleration of sample extraction (5 min instead of several hours), while total arsenic extraction efficiency is improved without species conversion. Validation was performed to evaluate the method for selectivity, linearity, LOD/LOQ (0.007-0.020 mg/kg), trueness, precision (HorRat values, 0.2-0.6), recovery (93-122%), and uncertainty. The method was also satisfactorily tested using two proficiency tests. Performance characteristics are reported for four certified reference materials, standard reference material (SRM) 1568a (rice flour), Institute for Reference Materials and Measurements 804 (rice flour), SRM 2976 (mussel tissue), certified reference material-627 (tuna fish), and several commercial food samples populating five AOAC triangle food sectors. The results indicated that this speciation method is cost-efficient, time-saving, and accurate, as well as fit-for-purpose, according to International Organization for Standardization/International Electrotechnical Commission 17025:2005 standard, and could be used for routine analysis.     

Single on-chip gold nanowires for electrochemical biosensing of glucose

The development of glucose diagnostic devices with low detection limits is of key importance in diabetes-related research. New highly sensitive sensors are required for non-invasive detection of glucose in bodily fluids, other than blood, and an electrochemical sensor based on a single gold nanowire for rapid, reliable and quantitative detection of low glucose concentrations (10 μM-1 mM), is presented in this paper. Single gold nanowire devices are fabricated at silicon chip substrates using a hybrid electron beam-photolithography approach. Critical dimensions of the nanowires are characterised using a combination of scanning electron and atomic force microscopies. Fabricated nanowire devices are characterised by direct electrical probing and cyclic voltammetry to explore functionality. The voltammetric detection of glucose was performed using ferrocene monocarboxylic acid as an oxidising mediator in the presence of glucose oxidase. The biosensor can be applied to the quantification of glucose in the range of 10 μM-100 mM, with an extremely high sensitivity of 7.2 mA mM(-1) cm(-2) and a low detection limit of 3 μM (S/N = 3). The sensor demonstrated high selectivity towards glucose with negligible interference from other oxidizable species including uric acid, ascorbic acid, mannose, fructose, salicylic acid (Aspirin) and acetaminophen (Paracetamol).     

Shades of green in 15th century paintings: combined microanalysis of the materials using synchrotron radiation XRD, FTIR and XRF

A representative selection of green paintings from fifteenth century Catalonia and the Crown of Aragon are analyzed by a combination of synchrotron radiation microanalytical techniques including FTIR, XRD, and XRF. The green pigments themselves are found to be a mixture of copper acetates/basic copper acetates and basic copper chlorides. Nevertheless, a broader range of green shades were obtained by mixing the green pigment with yellow, white, and blue pigments and applied forming a sequence of micrometric layers. Besides the nature of the pigments themselves, degradation and reaction products, such as carboxylates, formates and oxalates were also identified. Some of the copper based compounds, such as the basic copper chloride, may be either part of the original pigment or a weathering product. The high resolution, high brilliance, and small footprint of synchrotron radiation proved to be essential for the analysis of those submillimetric paint layers made of a large variety of compounds heterogeneous in nature and distribution and present in extremely low concentrations.     

Decarboxylative Amination of SMAHOs by Dialkyl Azodicarboxylates

The decarboxylative addition of substituted malonic acid half oxyesters (SMAHOs) to dialkyl azodicarboxylates is described. The reaction was promoted by 1,4-diazabicyclo[2.2.2]octane (DABCO) as an organocatalyst in heated toluene. High yields of the coupling products were generally obtained, and the scope of the reaction proved rather important with the potential presence of functionalized side chains at the α-position, affording an original access to α-aminoester derivatives.     

Radiative heat transfer at nanoscale: Closed-form expression for silicon at different doping levels

Radiative heat transfer at the nanoscale is becoming an important technological issue with the development of nano electromechanical systems (NEMS). In this article, we derive asymptotic expressions to compute near-field radiative heat transfer between two planes of silicon. We identify two physical mechanisms that give the dominant contribution at small gaps. For intrinsic and low-doped silicon, the main contribution is due to evanescent waves coming from propagating waves undergoing frustrated total internal reflections at the interfaces. For doping levels larger than N_e=10¹⁶ cm^?3 surface mode coupling contributes to the heat transfer. Asymptotic expressions are also given in that case. In all cases, we compare analytical formulas with exact numerical calculations when varying the temperature and the doping concentration. We also give their range of validity.     

Contribution to the solution of heisenberg's model for phase transitions in the presence of an external field: The A2 → B2 disorder-order transition in nonstoichiometric binary alloys

Abstract

In this article, the A2 → B2 transition is studied in nonstoichiometric binary alloys: Heisenberg's model for phase transitions in the presence of an external field is reduced to the resolution of a couple of differential equations. Introduction of the Gibbs grand canonical ensemble enables us to show that the interaction Hamiltonian between a pair ij and the rest of the crystal is written simply as ? _int =—μ[Ncirc] (where [Ncirc] is the particle number operator corresponding to the long-range-order parameter and μ is its intensive conjugate variable). Among others, the state vector and the density matrix of the pair ij, and the grand partition function are obtained as functions of the intensive variables of the problem. The long-range-order parameter is not a constant of the motion: it fluctuates with time in the vicinity of the transition.     

Optical fiber systems are convectively unstable

We theoretically and experimentally evidence that fiber systems are convective systems since their nonlocal inherent properties, such as the dispersion and Raman effects, break the reflection symmetry. Theoretical analysis and numerical simulations carried out for a fiber ring cavity demonstrate that the third-order dispersion term leads to the appearance of convective and absolute instabilities. Their signature is an asymmetry in the output power spectrum. Using this criterion, experimental evidence of convective instabilities is given in a fiber cavity pumped by a pulsed laser.     

Probing quantum-vacuum geometrical effects with cold atoms

The lateral Casimir-Polder force between an atom and a corrugated surface should allow one to study experimentally nontrivial geometrical effects in the electromagnetic quantum vacuum. Here, we derive the theoretical expression of this force in the scattering approach. We show that large corrections to the "proximity force approximation" could be measured using present-day technology with a Bose-Einstein condensate used as a vacuum field sensor.     

Laboratory demonstration of an infrared-to-visible up-conversion interferometer for spatial coherence analysis

We experimentally demonstrate the possibility of retrieving the spatial coherence of an infrared source by using an up-conversion interferometer. Sum-frequency generation in Ti-diffused periodically poled lithium-niobate waveguides in both arms of the interferometer is used to convert the infrared into the visible domain. The fringe contrast of the interference pattern in the visible domain permits us to resolve the spatial separation of two uncorrelated pointlike infrared sources, which simulate a binary star. The validity of these measurements is confirmed through a simultaneous comparison with a reference interferometer working in the infrared domain.