Enzymatic biosensor for the electrochemical detection of 2,4-dinitrotoluene biodegradation derivatives

In this work, we demonstrate for the first time that 4-methyl-5-nitrocatechol (4M5NC) and 2,4,5-trihydroxytoluene (2,4,5-THT), two compounds obtained from the 2,4-DNT biodegradation are recognized by polyphenol oxidase as substrates. An amperometric biosensor is described for detecting these compounds and for evaluating the efficiency of the 2,4-DNT conversion into 4M5NC in the presence of bacteria able to produce the 2,4-DNT-biotransformation. The biosensor format involves the immobilization of polyphenol oxidase into a composite matrix made of glassy carbon microspheres and mineral oil. The biosensor demonstrated to be highly sensitive for the quantification of 4M5NC and 2,4,5-THT. The analytical parameters for 4M5NC are the following: sensitivity of (7.5 ± 0.1) × 10⁵ nAM⁻¹, linear range between 1.0 × 10⁻⁵ and 8.4 × 10⁻⁵ M, and detection limit of 4.7 × 10⁻⁶ M. The sensitivity for the determination of 2,4,5-THT is (6.2 ± 0.6) × 10⁶ nAM⁻¹, with a linear range between 1.0 × 10⁻⁶ and 5.8 × 10⁻⁶ M, and a detection limit of 2.0 × 10⁻⁷. Under the experimental conditions, it was possible to selectively quantify 4M5NC even in the presence of a large excess of 2,4-DNT. The suitability of the biosensor for detecting the efficiency of 2,4-DNT biotransformation into 4M5NC is demonstrated and compared with HPLC-spectrophotometric detection, with very good correlation. This biosensor holds great promise for decentralized environmental testing of 2,4-DNT.     

Nanometer gold-silica composite particles manipulated by optical tweezers

We have studied the behavior of nano or micro size composite particles submitted to optical trapping forces and a comparison was made with homogeneous particles of similar dimension. The forces were measured using the power spectrum signal analysis. Most of the results presented were obtained using a lateral effect position sensitive detector (PSD), which allowed the fluctuations of the particle position in the optical trap to be monitored. A 4-quadrant photodiode was also used for the same purpose. We bring clear experimental evidence that the trapping force was increased by a factor of about 2-3 for composite particles made of a colloidal gold core encapsulated in a silica shell, with respect to homogeneous silica or latex beads. These results were discussed in the frame of the various approaches currently used for modeling optical tweezing forces.     

Testing equality between several populations covariance operators

In many situations, when dealing with several populations, equality of the covariance operators is assumed. An important issue is to study whether this assumption holds before making other inferences. In this paper, we develop a test for comparing covariance operators of several functional data samples. The proposed test is based on the Hilbert–Schmidt norm of the difference between estimated covariance operators. In particular, when dealing with two populations, the test statistic is just the squared norm of the difference between the two covariance operators estimators. The asymptotic behaviour of the test statistic under both the null hypothesis and local alternatives is obtained. The computation of the quantiles of the null asymptotic distribution is not feasible in practice. To overcome this problem, a bootstrap procedure is considered. The performance of the test statistic for small sample sizes is illustrated through a Monte Carlo study and on a real data set.     

A new reaction: lead(IV) acetate-mediated oxidative fragmentation of homoallylic alcohols

Treatment of a homoallylic alcohol with lead(IV) acetate in refluxing benzene for 2 hours results in an oxidative cleavage to give a carbonyl compound and an allylic acetate with high yield.     

Static fatigue lifetime of optical fibers in bending

An experimental program aimed at defining the effects of applied stress, temperature, humidity, and buffer coating on the static fatigue behavior of optical fibers in bending configurations is in progress. Data are presented below which demonstrate that the static fatigue behavior of fiber is strongly dependent on the polymeric buffer coating. Furthermore, the effect of humidity is readily evident by the comparison of times to failure at 30% RH and in water immersion. The ultimate objective of this research is to determine an allowable bend radius for fiber optic cable which is based on measurements of both static fatigue and strength in bending and which will assure reliable performance of the fiber over the design lifetime.     

Fredholm operator families —II

This paper is a continuation of a former one which has appeared in this journal. After considering (continuous and smooth) bundles of subspaces of an arbitrary topological vector space (tvs) we show how they appear naturally as image or kernel of semi-Fredholm families. We also extend some well known results of holomorphic Fredholm families to the setting of arbitrary tvs.     

Photochemical and nonphotochemical hole burning in dimethyl-s-tetrazine in a polyvinyl carbazole film

Hole burning as well as fluorescence line narrowing experiments have been performed on the system dimethyl-s-tetrazine in polyvinyl carbazole films at low temperatures. The first singlet electronic absorption bands are typical (300 cm^?3 wide) of inhomogeneously broadened bands of guest molecules in amorphous organic hosts. Evidence is presented for both photochemical and nonphotochemical hole burning. The narrowest holes observed were lorentzian, had a width of 0.44 cm^?1 at 1.8 K, and are believed to be of nonphotochemical origin. A model which envisions the guest molecules to occupy different sites in the polymer host with a distribution of energy barriers between sites is used to describe these observations. The fast (20 ps) relaxation time implied by the 0.44 cm^?1 lorentzian linewidth is interpreted as indicative of the rate of site interconversion in the excited state.     

Theoretical and experimental study of the catalytic cathodic stripping square-wave voltammetry of chromium species

The electrocatalytic mechanism of Cr(III) reduction in the presence of diethylenetriaminepentaacetic acid (DTPA) and nitrate ions is studied theoretically and experimentally by using stripping square-wave voltammetry (SWV). Experimental curves are in excellent agreement with theoretical profiles corresponding to a catalytic reaction of second kind. This type of mechanism is equivalent to a CE mechanism, where the chemical reaction produces the electroactive species. Accordingly, the reaction of Cr(III)–H₂O–DTPA and \( {\mathrm{NO}}_3^{-} \) would produce the electroactive species Cr(III)–NO₃–DTPA and this last species would release \( {\mathrm{NO}}_2^{-} \) to the solution during the electrochemical step. In this regard, the complex of Cr(III)–DTPA would work as the catalyzer that allows the reduction of \( {\mathrm{NO}}_3^{-} \) to \( {\mathrm{NO}}_2^{-} \). Furthermore, it was found that the electrochemical reaction is quite irreversible, with a constant of k _s?=?9.4?×?10^?5 cm s^?1, while the constant for the chemical step has been estimated to be k _chem?=?1.3?×?10⁴ s^?1. Considering that the equilibrium constant is K?=?0.01, it is possible to estimate the kinetic constants of the chemical reaction as k ₁?=?1?×?10² s^?1 and k _?1?=?1.29?×?10⁴ s^?1. These values of k ₁ and k _?1 indicate that the exchange of water molecules by nitrate is fast and that the equilibrium favors the complex with water. Also, a value for the formal potential E°’?≈??1.1 V was obtained. The model used for simulating experimental curves does not consider the adsorption of reactants yet. Accordingly, weak adsorption of reagents should be expected.     

Samarium/N-bromosuccinimide-induced reductive dimerization of carbonyl compounds

Stereoselective reductive coupling of carbonyl compounds has been achieved using samarium/N-bromosuccinimide in methanol. The combination of these agents has proved a powerful addition to the arsenal of samarium-based reductants currently utilized.