Facile and Low-Cost SPE Modification Towards Ultra-Sensitive Organophosphorus and Carbamate Pesticide Detection in Olive Oil

Despite the fact that a considerable amount of effort has been invested in the development of biosensors for the detection of pesticides, there is still a lack of a simple and low-cost platform that can reliably and sensitively detect their presence in real samples. Herein, an enzyme-based biosensor for the determination of both carbamate and organophosphorus pesticides is presented that is based on acetylcholinesterase (AChE) immobilized on commercially available screen-printed carbon electrodes (SPEs) modified with carbon black (CB), as a means to enhance their conductivity. Most interestingly, two different methodologies to deposit the enzyme onto the sensor surfaces were followed; strikingly different results were obtained depending on the family of pesticides under investigation. Furthermore, and towards the uniform application of the functionalization layer onto the SPEs’ surfaces, the laser induced forward transfer (LIFT) technique was employed in conjunction with CB functionalization, which allowed a considerable improvement of the sensor’s performance. Under the optimized conditions, the fabricated sensors can effectively detect carbofuran in a linear range from 1.1 × 10^?9 to 2.3 × 10^?8 mol/L, with a limit of detection equal to 0.6 × 10^?9 mol/L and chlorpyrifos in a linear range from 0.7 × 10^?9 up to 1.4 × 10^?8 mol/L and a limit of detection 0.4 × 10^?9 mol/L in buffer. The developed biosensor was also interrogated with olive oil samples, and was able to detect both pesticides at concentrations below 10 ppb, which is the maximum residue limit permitted by the European Food Safety Authority.     

On set theoretic complete intersections in P k 3

We prove that smooth monomial curves of degree greater than three are not set theoretic complete intersections on a wide class of surfaces, called bihonogeneous surfaces.     

The solution of the linear complementarity problem by the matrix analogue of the accelerated overrelaxation iterative method

The Linear Complementarity Problem (LCP), with an H₊?matrix coefficient, is solved by using the new “(Projected) Matrix Analogue of the AOR (MAAOR)” iterative method; this new method constitutes an extension of the “Generalized AOR (GAOR)” iterative method. In this work two sets of convergence intervals of the parameters involved are determined by the theories of “Perron-Frobenius” and of “Regular Splittings”. It is shown that the intervals in question are better than any similar convergence intervals found so far by similar iterative methods. A deeper analysis reveals that the “best” values of the parameters involved are those of the (projected) scalar Gauss-Seidel iterative method. A theoretical comparison of the “best” (projected) Gauss-Seidel and the “best” modulus-based splitting Gauss-Seidel method is in favor of the former method. A number of numerical examples support most of our theoretical findings.     

Ab initio study of the electronic structure and bonding of aluminum nitride

For the diatomic aluminum nitride (AlN), we have constructed potential energy curves for 45 states employing multi-reference variational methods and quantitative basis sets. Thirty-six states are relatively strongly bound, five present local minima, and four are of repulsive nature. Almost all states are of intense multi-reference character rendering their calculation and interpretation quite problematic. Our tentative assignment of the ground state is 3Pi, while a 3Sigma- state is above by less than 1 kcal/mol. Our best estimate for the binding energy of the X3Pi state is D0 = 56.0 +/- 0.5 kcal/mol at re = 1.783 A, in good agreement with the experimental values of D = 66 +/- 9 kcal/mol and re = 1.7864 A. The binding energy of the A3Sigma- state is very similar to the X state because they both correlate to the ground-state atoms, but the bond distance of the former is 0.13 A longer. The first seven states can be tagged as follows: X3Pi, A3Sigma-, a1Sigma+, b1Pi, c1Delta, B3Sigma+, and d1Sigma+, a rather definitive order with the exception of X and A states.     

On the average volume of sections of convex bodies

The average section functional as(K) of a star body in Rn is the average volume of its central hyperplane sections: \(as\left( k \right) = \int_{{S^{n - 1}}} {\left| {K \cap {\xi ^ \bot }} \right|} d\sigma \left( \xi \right)\). We study the question whether there exists an absolute constantC > 0 such that for every n, for every centered convex body K in R ⁿ and for every 1 ≤ k ≤ n ? 2,

$$as\left( K \right) \leqslant {C^k}{\left| K \right|^{\frac{k}{n}}}\mathop {\max }\limits_{|E \in G{r_{n - k}}} {\kern 1pt} as\left( {K \cap E} \right)$$

. We observe that the case k = 1 is equivalent to the hyperplane conjecture. We show that this inequality holds true in full generality if one replaces C by CL _K orCd_ovr(K, BP _k ⁿ ), where L _K is the isotropic constant of K and dovr(K, BP _k ⁿ ) is the outer volume ratio distance of K to the class BP _k ⁿ of generalized k-intersection bodies. We also compare as(K) to the average of as(K ∩ E) over all k-codimensional sections of K. We examine separately the dependence of the constants on the dimension when K is in some classical position. Moreover, we study the natural lower dimensional analogue of the average section functional.

     

Minimal systems of binomial generators and the indispensable complex of a toric ideal

Let be a vector configuration and its corresponding toric ideal. The paper consists of two parts. In the first part we completely determine the number of different minimal systems of binomial generators of . In the second part we associate to a simplicial complex . We show that the vertices of correspond to the indispensable monomials of the toric ideal , while one dimensional facets of with minimal binomial -degree correspond to the indispensable binomials of .

     

Ultrasensitive Determination of Vitamin B12 Using Disposable Graphite Screen‐Printed Electrodes and Anodic Adsorptive Voltammetry

A facile, rapid and ultra‐sensitive method for the determination of vitamin B₁₂ (cyanocobalamin) at the sub‐nanomolar concentration range by using low‐cost, disposable graphite screen‐printed electrodes is described. The method is based on the cathodic preconcentration of square planar vitamin B_12s, as occurred due to the electro reduction of Co(III) center in vitamin B_12a to Co(I), at ?1.3 V versus Ag/AgCl/3 M KCl for 40 s. Then, an anodic square wave scan was applied and the height of the peak appeared at ca. ?0.73 V versus Ag/AgCl/3 M KCl, due to the oxidation of Co(I) to Co(II) in the adsorbed molecule, was related to the concentration of the vitamin B₁₂ in the sample. EDTA was found to serve as a key‐component of the electrolyte by eliminating the background signal caused by metal cations impurities contained in the electrolyte (0.1 M phosphate buffer in 0.1 M KCl, pH 3). It also blocks trace metals contained in real samples, thus eliminating their interference effect. The method was optimized to various working parameters and under the selected conditions the calibration curve was linear over the range 1×10^?10–8×10^?9 mol L^?1 vitamin B₁₂ (R²=0.994), while the limit of detection for a signal‐to‐noise ratio of 3 (7×10^?11 mol L^?1 vitamin B₁₂) is the lowest value of any reported in the literature for the electrochemical determination of vitamin B₁₂. The sensors were successfully applied to the determination of vitamin B₁₂ in pharmaceutical products.     

Theoretical investigation of the He-I2(E3Πg) ion-pair state: ab initio intermolecular potential and vibrational levels

We present a theoretical study on the potential energy surface and vibrational bound states of the E electronic excited state of the HeI(2) van der Waals system. The interaction energies are computed using accurate ab initio methods and large basis sets. Relativistic small-core effective core potentials in conjunction with a quintuple-zeta quality basis set are employed for the heavy iodine atoms in multireference configuration interaction calculations for the (3)A' and (3)A" states. For the representation of the potential energy surface we used a general interpolation technique for constructing potential surfaces from ab initio data based on the reproducing kernel Hilbert space method. The surface presents global and local minima for T-shaped configurations with well-depths of 33.2 and 4.6 cm(-1), respectively. Vibrational energies and states are computed through variational quantum mechanical calculations. We found that the binding energy of the HeI(2)(E) T-shaped isomer is 16.85 cm(-1), in excellent agreement with recent experimental measurements. In lieu of more experimental data we also report our predictions on higher vibrational levels and we analyze the influence of the underlying surface on them. This is the first attempt to represent the potential surface of such a highly excited electronic state of a van der Waals complex, and it demonstrates the capability of the ab initio technology to provide accurate results for carrying out reliable studies to model experimental data.     

An ab initio study of the E 3Πg state of the iodine molecule

The E (3)Π(g) state of the iodine molecule is studied by ab initio multireference methods coupled with effective core potentials and large basis sets. Two potential minima are found, a global featuring an ion-pair character, and a local presenting a purely Rydberg nature. Four avoided crossings along the dissociation coordinate attribute an interesting topology to its potential energy curve, and their effect on the vibrational levels of I(2) is discussed.     

Specializations of Multigradings and the Arithmetical Rank of Lattice Ideals

In this article, we study specializations of multigradings and apply them to the problem of the computation of the arithmetical rank of a lattice ideal I _{L 𝒢}  ? K[x ₁,…, x _n ]. The arithmetical rank of I _{L 𝒢} equals the ?-homogeneous arithmetical rank of I _{L 𝒢} , for an appropriate specialization ? of 𝒢. To the lattice ideal I _{L 𝒢} and every specialization ? of 𝒢, we associate a simplicial complex. We prove that combinatorial invariants of the simplicial complex provide lower bounds for the ?-homogeneous arithmetical rank of I _{L 𝒢} .