Voltammetric Sensing of Mercury and Copper Cations at Poly(EDTA‐like) Film Modified Electrode

Complexing polymer‐coated electrodes have been synthesized by oxidative electropolymerization of ethylenediamine tetra‐N‐(3‐pyrrole‐1‐yl)propylacetamide (monomer L ). The presence of four polymerizable pyrrole fragments on the same EDTA skeleton was thought to confer enhanced rigidity and controlled dimensionality to the resulting complexing materials, which were used for the electrochemical detection of Hg(II), Cu(II), Pb(II) and Cd(II) ions by means of the chemical preconcentration‐anodic stripping technique. The polyamide electrode material showed particularly a significant selectivity towards mercury ions, even in the presence of a large excess of other metal cations. Moreover, the use of imprinted polymer‐coated electrodes prepared by electropolymerization of L in the presence of metal cations turned out to significantly improve the detection limits, down to 5×10^?10 mol L^?1 for Hg(II) and Cu(II) species.     

Novel nanocomposite membranes from cellulose acetate and clay‐silica nanowires

In this study, a new class of heterogeneous membranes based on cellulose acetate (CA) polymer and a complex filler clay‐silica nanowires (SiO₂NWs) was investigated for potential biomedical applications. SiO₂NWs were synthesized using natural clay through a facile sol–gel method and were dispersed in the polymer solution by sonication in the 1.25, 2.5, and 5% weight ratio to the CA acetate polymer. Membranes were subsequently prepared via phase inversion by precipitation of the CA polymer in water. The pristine CA membrane and SiO₂NWs based nanocomposites membranes were characterized using different characterization techniques. The presence of the SiO₂NWs in the CA membrane was found to significantly enhance the protein retention, water wettability and thermal as well as mechanical properties in comparison to the pristine CA membrane. Water flows studies at different temperatures and the retention of bovine serum albumin have been studied and the nanocomposite membranes were found to exhibit superior performances compared with the pristine CA membranes. SiO₂NWs‐CA membranes showed a much higher stability to the water temperature change during separation than CA membranes. Morphological changes clearly revealed that the composite membrane were much more compact than the pristine CA membranes. The rabbit dermal fibroblasts cell viability in cultures after 72 hr of incubation was found to be greater than 80%. These newly synthesized composite membranes exhibit a high potential to be used for various medical applications because of their non‐cytotoxic characteristics. Copyright © 2016 John Wiley & Sons, Ltd.     

Toward the computer-aided discovery of FabH inhibitors. Do predictive QSAR models ensure high quality virtual screening performance?

Antibiotic resistance has increased over the past two decades. New approaches for the discovery of novel antibacterials are required and innovative strategies will be necessary to identify novel and effective candidates. Related to this problem, the exploration of bacterial targets that remain unexploited by the current antibiotics in clinical use is required. One of such targets is the \(\beta \) -ketoacyl-acyl carrier protein synthase III (FabH). Here, we report a ligand-based modeling methodology for the virtual-screening of large collections of chemical compounds in the search of potential FabH inhibitors. QSAR models are developed for a diverse dataset of 296 FabH inhibitors using an in-house modeling framework. All models showed high fitting, robustness, and generalization capabilities. We further investigated the performance of the developed models in a virtual screening scenario. To carry out this investigation, we implemented a desirability-based algorithm for decoys selection that was shown effective in the selection of high quality decoys sets. Once the QSAR models were validated in the context of a virtual screening experiment their limitations arise. For this reason, we explored the potential of ensemble modeling to overcome the limitations associated to the use of single classifiers. Through a detailed evaluation of the virtual screening performance of ensemble models it was evidenced, for the first time to our knowledge, the benefits of this approach in a virtual screening scenario. From all the obtained results, we could arrive to a significant main conclusion: at least for FabH inhibitors, virtual screening performance is not guaranteed by predictive QSAR models.     

A preconditioning technique for Schur complement systems arising in stochastic optimization

Deterministic sample average approximations of stochastic programming problems with recourse are suitable for a scenario-based parallelization. In this paper the parallelization is obtained by using an interior-point method and a Schur complement mechanism for the interior-point linear systems. However, the direct linear solves involving the dense Schur complement matrix are expensive, and adversely affect the scalability of this approach. We address this issue by proposing a stochastic preconditioner for the Schur complement matrix and by using Krylov iterative methods for the solution of the dense linear systems. The stochastic preconditioner is built based on a subset of existing scenarios and can be assembled and factorized on a separate process before the computation of the Schur complement matrix finishes on the remaining processes. The expensive factorization of the Schur complement is removed from the parallel execution flow and the scaling of the optimization solver is considerably improved with this approach. The spectral analysis indicates an exponentially fast convergence in probability to 1 of the eigenvalues of the preconditioned matrix with the number of scenarios incorporated in the preconditioner. Numerical experiments performed on the relaxation of a unit commitment problem show good performance, in terms of both the accuracy of the solution and the execution time.     

Efficient hydroxycarbonylation of aryl iodides using recoverable and reusable carbon aerogels doped with palladium nanoparticles as catalyst

Electron-rich and electron-poor aryl iodides are converted, in high to excellent yields, into the corresponding carboxylic acids through a hydroxycarboxylation reaction catalyzed by a recoverable and reusable phosphine free palladium-carbon aerogel catalyst using lithium formate and acetic anhydride as an internal condensed source of carbon monoxide. The catalyst system can be reused several times without any appreciable loss of activity.     

Optimal control of linear stochastic evolution equations in Hilbert spaces and uniform observability

In this paper we study the existence of the optimal (minimizing) control for a tracking problem, as well as a quadratic cost problem subject to linear stochastic evolution equations with unbounded coefficients in the drift. The backward differential Riccati equation (BDRE) associated with these problems (see [2], for finite dimensional stochastic equations or [21], for infinite dimensional equations with bounded coefficients) is in general different from the conventional BDRE (see [10], [18]). Under stabilizability and uniform observability conditions and assuming that the control weight-costs are uniformly positive, we establish that BDRE has a unique, uniformly positive, bounded on ℝ ₊ and stabilizing solution. Using this result we find the optimal control and the optimal cost. It is known [18] that uniform observability does not imply detectability and consequently our results are different from those obtained under detectability conditions (see [10]).      

Minimal condition number for positive definite Hankel matrices using semidefinite programming

We present a semidefinite programming approach for computing optimally conditioned positive definite Hankel matrices of order n. Unlike previous approaches, our method is guaranteed to find an optimally conditioned positive definite Hankel matrix within any desired tolerance. Since the condition number of such matrices grows exponentially with n, this is a very good test problem for checking the numerical accuracy of semidefinite programming solvers. Our tests show that semidefinite programming solvers using fixed double precision arithmetic are not able to solve problems with n>30. Moreover, the accuracy of the results for 24?n?30 is questionable. In order to accurately compute minimal condition number positive definite Hankel matrices of higher order, we use a Mathematica 6.0 implementation of the SDPHA solver that performs the numerical calculations in arbitrary precision arithmetic. By using this code, we have validated the results obtained by standard codes for n?24, and we have found optimally conditioned positive definite Hankel matrices up to n=100.     

Compact eye-safe laser sources based on OPOs with KTP or PPKTP crystals

We report on compact eye-safe nanosecond laser sources emitting in the 1.5 μm wavelength range based on non-critically phase-matched parametric interaction in optical parametric oscillators (OPOs) with KTP and periodically poled KTP (PPKTP) crystals, pumped by the fundamental frequency of Nd:YAG lasers. As much as 250 μJ signal pulse energy at 1.5 μm wavelength, 6.5 ns FWHM pulse-width, has been obtained in a PPKTP-OPO, extracavity pumped by a Nd:YAG microlaser oscillator–amplifier at 650 μJ pump pulse energy, 8 ns pulse-width. A single signal pulse of 2.7-mJ output energy at 1.57 μm wavelength, less than 5 ns pulse-width, was generated in a KTP-OPO, intracavity pumped by a passively Q-switched Nd:YAG laser.