Simultaneous Anodic Stripping Voltammetric Determination of Pb and Cd,Using a Vibrating Gold Microwire Electrode,Assisted by Chemometric Techniques

Simultaneous anodic stripping voltammetric determination of Pb and Cd is restricted on gold electrodes as a result of the overlapping of these two peaks. This work describes the quantitative determination of a binary mixture system of Pb and Cd, at low concentration levels (up to 15.0 and 10.0 µg L^?1 for Pb and Cd, respectively) by differential pulse anodic stripping voltammetry (DPASV; deposition time of 30 s), using a green electrode (vibrating gold microwire electrode) without purging in a chloride medium (0.5 M NaCl) under moderate acidic conditions (HCl 1.0 mM), assisted by chemometric tools. The application of multivariate curve resolution alternating least squares (MCR‐ALS) for the resolution and quantification of both metals is shown. The optimized MCR‐ALS models showed good prediction ability with concentration prediction errors of 12.4 and 11.4 % for Pb and Cd, respectively. The quantitative results obtained by MCR‐ALS were compared to those obtained with partial least squares (PLS) and classical least squares (CLS) regression methods. For both metals, PLS and MCR‐ALS results are comparable and superior to CLS. For Cd, as a result of the peak shift problem, the application of CLS was unsuitable. MCR‐ALS provides additional advantage compared to PLS since it estimates the pure response of the analytes signal. Finally, the built up multivariate calibration models, based either in MCR‐ALS or PLS regression, allowed to quantify concentrations of Pb and Cd in surface river water samples, with satisfactory results.     

Extension and application of multivariate curve resolution-alternating least squares to four-way quadrilinear data-obtained in the investigation of pollution patterns on Yamuna River,India—A case study

This study focuses on the development and extension of Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) to the analysis of four-way datasets. The proposed extension of the MCR-ALS method with non-negativity and the newly developed quadrilinear constraints can be exploited to summarize and manage huge multidimensional datasets and resolve their four way component profiles. In this study, its application is demonstrated by analyzing a four-way data set obtained in a long term environmental monitoring study (15 sampling sites × 9 variables × 12 months × 7 years) belonging to the Yamuna River, one of the most polluted rivers of India and the largest tributary of the Ganges river. MCR-ALS resolved pollution profiles described appropriately the major observed changes on pH, organic pollution, bacteriological pollution and temperature, along with their spatial and temporal distribution patterns for the studied stretch of Yamuna River. Results obtained by MCR-ALS have also been compared with those obtained by another multi-way method, PARAFAC. The methodology used in this study is completely general and it can be applied to other multi-way datasets.     

Irradiance dependence of the He-Ne laser-induced protection against UVC radiation in E. coli strains

He-Ne laser pre-irradiation-induced protection against UVC damage was investigated in wild-type E. coli K12 strain AB1157 and its isogenic DNA repair mutant strains. At a dose of 7 kJ/m(2), pre-irradiation was observed to induce protection in recA proficient strains (AB1157 and uvrA(-) AB1886) at both the irradiances investigated (2 and 100 W/m(2)). However, at the same dose (7 kJ/m(2)), while no protection was observed at 100 W/m(2) in the recA(-) strain, some protection appeared to be there at 2 W/m(2). Mechanistic studies carried out on these strains at the two irradiances suggest that, whereas the protection observed at 100 W/m(2) is mediated by singlet oxygen, that observed at 2 W/m(2) is not. Further, the fact that protection at 100 W/m(2) was observed only in recA proficient strains suggests that it may arise due to the induction of DNA repair processes controlled by the recA gene. The latter may arise due to the oxidative stress produced by singlet oxygen generated by He-Ne laser irradiation. In contrast, the protection observed at 2 W/m(2) appears to be independent of the DNA repair proficiency of the strain.     

Carbohydrates as building blocks of privileged ligands

“Privileged ligands” are chiral auxiliaries of wide applicability in asymmetric catalysis. In the previous decades, their effective three-dimensional structures have often been reproduced by using building blocks from a “chiral pool”, such as the carbohydrates. This strategy has provided unique ligand moieties which combine the performance of “privileged ligands” with increased flexibility and accessibility. This review gives an overview of the research within this field, giving emphasis to the best results obtained with each ligand type.     

Exploiting damped techniques for nonlinear conjugate gradient methods

In this paper we propose the use of damped techniques within Nonlinear Conjugate Gradient (NCG) methods. Damped techniques were introduced by Powell and recently reproposed by Al-Baali and till now, only applied in the framework of quasi-Newton methods. We extend their use to NCG methods in large scale unconstrained optimization, aiming at possibly improving the efficiency and the robustness of the latter methods, especially when solving difficult problems. We consider both unpreconditioned and Preconditioned NCG. In the latter case, we embed damped techniques within a class of preconditioners based on quasi-Newton updates. Our purpose is to possibly provide efficient preconditioners which approximate, in some sense, the inverse of the Hessian matrix, while still preserving information provided by the secant equation or some of its modifications. The results of an extensive numerical experience highlights that the proposed approach is quite promising.     

Multinuclear solid state NMR investigation of two polymorphic forms of ciprofloxacin-saccharinate

Two polymorphic forms of a novel pharmaceutical compound, ciprofloxacin-saccharinate (CIP-SAC), are analyzed using one dimensional (1D) and two dimensional (2D) (1)H nuclear magnetic resonance (NMR) at fast magic angle spinning (MAS). Additionally (15)N spectroscopy and (1)H-(13)C correlation experiments were performed to complement our conclusions. The 1D (1)H NMR spectra of CIP and complexes reveal valuable information about the ionic bonding between ciprofloxacin and saccharine. Additionally, these spectra allow us to perform a clear characterization of each solid form, giving the number of molecules per unit cell in one of the polymorphs. From 2D (1)H-(1)H spectra obtained through double quantum correlations we can arrive at important conclusions about the hydrogen bonding, conformation, and intra and inter-molecular interactions present in these compounds. Comparing and contrasting the (1)H-(1)H correlation data obtained for both polymorphic forms and taking into account the single crystal structure data existing for the solid form CIP-SAC (II) was possible to extract some conclusions on the polymorph CIP-SAC (I) where no single crystal information is available. (1)H MAS NMR is shown to be an important tool in the field of polymorphism and for the characterization of multicomponent pharmaceutical compounds.     

On mixed joint discrete universality for a class of zeta-functions. II

We investigate the mixed joint discrete value distribution and the mixed joint discrete universality for the pair consisting of a rather general form of zeta-function with an Euler product and a periodic Hurwitz zeta-function with transcendental parameter. The common differences of relevant arithmetic progressions are not necessarily the same. Also some generalizations are given. For this purpose, certain arithmetic conditions on the common differences are used.

     

An adaptive truncation criterion,for linesearch-based truncated Newton methods in large scale nonconvex optimization

Starting from the paper by Nash and Sofer (1990), we propose a heuristic adaptive truncation criterion for the inner iterations within linesearch-based truncated Newton methods. Our aim is to possibly avoid “over-solving” of the Newton equation, based on a comparison between the predicted reduction of the objective function and the actual reduction obtained. A numerical experience on unconstrained optimization problems highlights a satisfactory effectiveness and robustness of the adaptive criterion proposed, when a residual-based truncation criterion is selected.     

Numerical Experiences with New Truncated Newton Methods in Large Scale Unconstrained Optimization

Recently, in [12] a very general class oftruncated Newton methods has been proposed for solving large scale unconstrained optimization problems. In this work we present the results of an extensive numericalexperience obtained by different algorithms which belong to the preceding class. This numerical study, besides investigating which arethe best algorithmic choices of the proposed approach, clarifies some significant points which underlies every truncated Newton based algorithm.     

Mechanism of copper underpotential deposition at Pt(<Emphasis Type="Italic">hkl</Emphasis>)-electrodes: Quantum-chemical modelling

Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption.