Recent developments in handheld and portable optosensing-a review

Recent developments in portable and handheld opto-chemical analytical instrumentation over the last decade (2000-2010) are reviewed. First, the characteristics of typical portable/handheld instrumentation are discussed from different points of view: in situ operation, low energy consumption, ease of use, and self-contained devices. These advancements have improved or hastened improvements in the development of miniaturized optoelectronic and optical components, mainly solid-state devices such as different types of semiconductor lasers, light-emitting diodes, and photodiodes. A brief review of advances in these components is also presented. The numerous examples of portable instrumentation presented have been classified according to direct-recognition and reagent-based sensing, and within these, by absorption and emission-based systems. The conclusion discusses some key trends and future perspectives for this technology.     

Numerical method for coupling the macro and meso scales in stochastic chemical kinetics

A numerical method is developed for simulation of stochastic chemical reactions. The system is modeled by the Fokker–Planck equation for the probability density of the molecular state. The dimension of the domain of the equation is reduced by assuming that most of the molecular species have a normal distribution with a small variance. The numerical approximation preserves properties of the analytical solution such as non-negativity and constant total probability. The method is applied to a nine dimensional problem modelling an oscillating molecular clock. The oscillations stop at a fixed point with a macroscopic model but they continue with our two dimensional, mixed macroscopic and mesoscopic model. Dedicated to the memory of Germund Dahlquist (1925–2005). AMS subject classification (2000)  65M20, 65M60     

Conservative solution of the Fokker–Planck equation for stochastic chemical reactions

In this paper we discuss multigrid methods for ill-conditioned symmetric positive definite block Toeplitz matrices. Our block Toeplitz systems are general in the sense that the individual blocks are not necessarily Toeplitz, but we restrict our attention to blocks of small size. We investigate how transfer operators for prolongation and restriction have to be chosen such that our multigrid algorithms converge quickly. We point out why these transfer operators can be understood as block matrices as well and how they relate to the zeroes of the generating matrix function. We explain how our new algorithms can also be combined efficiently with the use of a natural coarse grid operator. We clearly identify a class of ill-conditioned block Toeplitz matrices for which our algorithmic ideas are suitable. In the final section we present an outlook to well-conditioned block Toeplitz systems and to problems of vector Laplace type. In the latter case the small size blocks can be interpreted as degrees of freedom associated with a node. A large number of numerical experiments throughout the article confirms convincingly that our multigrid solvers lead to optimal order convergence. AMS subject classification (2000) 65N55, 65F10     

Revisitation of the phenylisothiocyanate‐derivatives procedure for amino acid determination by HPLC‐UV

A revisitation of the well known chromatographic procedure for the determination of amino acids as phenylthiocarbamyl derivatives (PTC) is performed. The method was developed for a microbore column that it is more appropriate to our later aims, the characterization of proteinaceous binders present in microsamples coming from the Cultural Heritage field. Several variables relating to chromatographic aspects were studied such as the pH and temperature of the mobile phase, buffer and modifier (triethylamine) concentrations in mobile phase and the stability of PTC‐derivatives in solution. The calibration function was studied in depth. To prevent the heteroscedastic behaviour that it is observed, we used the weighed least squares fitting as the best strategy among other normalizing transformations, such as square root and logarithmic functions. Finally, the proposed method showed results similar to the traditional method in terms of efficiency, runtime, LODs and other characteristics, but with two additional advantages: a lower mobile phase consumption and the possibility of working with a lower sample volume. The usefulness of proposed method is checked against easel painting samples of Pictorial Heritage.     

Determination of gentamicin in pharmaceutical formulations using peroxyoxalate chemiluminescent detection in flow-injection analysis

A simple and sensitive procedure for the determination of gentamicin is presented, based on the use of the peroxyoxalate chemiluminescent (PO-CL) system in presence of imidazole as a catalyst. The gentamicin has to be previously derivatized with o-phthaladehyde (OPA) in order to obtain a fluorophore, which participates in the PO reaction, producing a CL emission proportional to the gentamicin concentration. The method is developed by using a particular flow-injection analysis (FIA) manifold, employing sodium dodecyl sulfate (SDS) micellar medium as a carrier in order to avoid the degradation of PO in water. The optimization of the instrumental and chemical variables affecting the CL reaction was rigorously carried out by using experimental design methodology. The method has been successfully applied to pharmaceutical formulations.     

Calculating initial-state-selected reaction probabilities from thermal flux eigenstates: a transition-state-based approach

An approach for the calculation of initial-state-selected reaction probabilities utilizing a transition-state view and the multiconfigurational time-dependent Hartree approach is presented. Using flux correlation functions, wave packets located in the transition-state region are constructed and propagated into the asymptotic region to obtain initial-state-selected reaction probabilities. A complete set of reaction probabilities is obtained from a single set of thermal flux eigenstates. Concepts previously applied with success to the calculation of k(T) or N(E) are transferred to the calculation of state-selected probabilities. The benchmark H+H(2) (J=0) reaction on the LSTH potential-energy surface is used to test the reliability of this approach.     

Photocurrent responses at dye sensitised ultrathin polyelectrolyte multilayers supported on gold electrodes

The photoelectrochemical behaviour of ionic conducting ultrathin multilayers formed by sequential deposition of poly-L-lysine and poly-L-glutamic acid on modified gold electrodes is investigated upon sensitisation by zinc mesotetrakis(p-sulfonatophenyl)porphyrin.     

Simultaneous determination of tartrazine and sunset yellow in cosmetic products by first-derivative spectrophotometry

A spectrophotometric method for the simultaneous determination of Tartrazine (TT) and Sunset Yellow (SY) in cosmetic products has been developed. An extraction process was carried out using methylene chloride and the colouring matters were measured in the aqueous phase formed, the other components of the sample remaining in the organic phase. The applicable concentration ranges were 0.5–10 ug/ml TT and 0.5–12 g/ml SY. The detection limits were 26 and 11 ng/ml and the relative standard deviations were 1.0 and 0.9% for TT and SY, respectively. The method was applied to the determination of both compounds in cosmetics.     

Multicolor fluorescence imaging of leaves--a useful tool for visualizing systemic viral infections in plants

Abstract Multicolor fluorescence induced by UV light is a sensitive and specific tool that may be used to provide information about the primary and secondary metabolism of plants by monitoring signals of the chlorophyll fluorescence (Chl-F) and blue-green fluorescence (BGF), respectively. We have followed the systemic infection of Nicotiana benthamiana plants with the Pepper mild mottle virus (PMMoV) by means of a multicolor fluorescence-imaging system, to detect differences between two strains of PMMoV during the infection process and to establish a correlation between the virulence and changes induced in the host plant. Changes in both BGF and Chl-F were monitored. BGF increased mainly in the abaxial side of the leaf during pathogenesis and the corresponding images showed a clear vein-associated pattern in leaves of infected plants. HPLC analysis of leaf extracts was carried out to identify compounds emitting BGF, and determined that chlorogenic acid was one of the main contributors. BGF imaging was able to detect viral-induced changes in asymptomatic (AS) leaves before detection of the virus itself. Chl-F images confirmed our previous results of alterations in the photosynthetic apparatus of AS leaves from infected plants that were detected with other imaging techniques. Fluorescence ratios F440/F690 and F440/F740, which increase during pathogenesis, were excellent indicators of biotic stress.