An on-line potentiometric sequential injection titration process analyser for the determination of acetic acid

An on-line potentiometric sequential injection titration process analyser for the determination of acetic acid is proposed. A solution of 0.1 mol L(-1) sodium chloride is used as carrier. Titration is achieved by aspirating acetic acid samples between two strong base-zone volumes into a holding coil and by channelling the stack of well-defined zones with flow reversal through a reaction coil to a potentiometric sensor where the peak widths were measured. A linear relationship between peak width and logarithm of the acid concentration was obtained in the range 1-9 g/100 mL. Vinegar samples were analysed without any sample pre-treatment. The method has a relative standard deviation of 0.4% with a sample frequency of 28 samples per hour. The results revealed good agreement between the proposed sequential injection and an automated batch titration method.     

Diamond paste-based electrodes for determination of Cr(III) in pharmaceutical compounds

A new class of monocrystalline diamond paste-based electrodes is proposed for the determination of chromium(III) at trace levels in vitamins. Three types of monocrystalline diamond—natural diamond 1 (natural diamond), synthetic diamond 50 (synthetic-1), and synthetic diamond 1 (synthetic-2)—were used for electrode construction. The linear concentration ranges are between 10^–10 and 10^–8; 10^–9 and 10^–7, and 10^–10 to 10^–8 mol L^–1, with limits of detection of 10^–12, 10^–12, and 10^–11 mol L^–1, when natural diamond, synthetic-1, and synthetic-2, respectively, are used as electrode materials. For electrodes based on natural diamond and synthetic-1 it was found that Cr(III) yields a peak at about +0.275±0.015 V (vs. Ag/AgCl) within a predetermined positive potential range situated between +0.4 and +0.2 V, while for the electrode based on synthetic-2 the peaks are found at +0.300±0.015 V (vs. Ag/AgCl). The proposed method is reliable for the determination of chromium(III) at trace levels in two vitamin tablets (RSD<0.2%).     

Heterogeneous diastereoselective hydrogenation of pyridine and corresponding enamine covalently bound to pantolactone

The diastereoselective hydrogenation of 2-methyl nicotinic acid covalently bound to pantolactone was studied over supported metallic catalysts. With this chiral auxiliary, a two-steps reaction was observed with formation of tetrahydropyridine intermediate. The influence of different reaction parameters on the diastereoselectivity of the hydrogenation of pyridine and enamine substrates was studied.     

Noniterative biexponential fluorescence lifetime imaging in the investigation of cellular metabolism by means of NAD(P)H autofluorescence.

The cofactors NADH and NADPH, hereafter NAD(P)H [NAD(P)= nicotinamide adenine dinucleotide (phosphate)], belong to the principal endogenous indicators of energetic cellular metabolism. Since the metabolic activity of cells is given by the ratio between the concentrations of free and protein-bound NAD(P)H, the development of autofluorescence techniques which accurately measure the modifications to this ratio is particularly significant. Hitherto the methods applied in the monitoring of cellular metabolism have provided either imprecise results, due to interference of the NAD(P)H signal by perturbing factors, or they have required a complicated internal calibration. We employ biexponential fluorescence lifetime imaging (FLIM) in order to discriminate between the free and protein-bound NAD(P)H without any previous calibration. Thus, we have obtained directly, and for the first time, a high-resolution map of cellular metabolism, that is, an image of the contribution of the protein-bound NAD(P)H to the cumulative NAD(P)H fluorescence signal. Moreover, we demonstrate that protein-NAD(P)H complexes characterised by different fluorescence lifetimes are not uniformly distributed all over the cell, as assumed until now, but are concentrated in certain cellular regions. The different fluorescence lifetimes indicate either different protein-NAD(P)H complexes or different bond strengths between NAD(P)H and the protein in these complexes. Since an important aspect in biological applications is to monitor the dynamics of the relevant processes (such as cellular metabolism), rapid dynamical techniques, for example, rapid biexponential fluorescence lifetime imaging, are needed. Furthermore, it is necessary to reduce the evaluation effort as much as possible. Most of the evaluation techniques in multiexponential FLIM are time-expensive iterative methods. The few exceptions are connected with a loss of information, for example, global analysis; or a loss in accuracy, for example, the rapid evaluation technique (RLD). We implement for the first time in FLIM a noniterative, nonrestrictive method originally developed by Prony for approximations of multiexponential decays. The accuracy of this method is verified in biexponential FLIM experiments in time-domain on mixtures of two chromophores both in homogenous and in heterogeneous media. The resulting fluorescence lifetimes agree (within error margins) with the lifetimes of the pure substances determined in monoexponential FLIM experiments. The rapidity of our evaluation method as compared to iterative pixel-by-pixel methods is evidenced by a reduction of the evaluation time by more than one order of magnitude. Furthermore, the applicability of this method for the biosciences is demonstrated in the investigation of cellular metabolism by means of NAD(P)H endogenous fluorescence.     

The Effect of Calcium-Silicate Cements on Reparative Dentinogenesis Following Direct Pulp Capping on Animal Models

Dental pulp vitality is a desideratum for preserving the health and functionality of the tooth. In certain clinical situations that lead to pulp exposure, bioactive agents are used in direct pulp-capping procedures to stimulate the dentin-pulp complex and activate reparative dentinogenesis. Hydraulic calcium-silicate cements, derived from Portland cement, can induce the formation of a new dentin bridge at the interface between the biomaterial and the dental pulp. Odontoblasts are molecularly activated, and, if necessary, undifferentiated stem cells in the dental pulp can differentiate into odontoblasts. An extensive review of literature was conducted on MedLine/PubMed database to evaluate the histological outcomes of direct pulp capping with hydraulic calcium-silicate cements performed on animal models. Overall, irrespective of their physico-chemical properties and the molecular mechanisms involved in pulp healing, the effects of cements on tertiary dentin formation and pulp vitality preservation were positive. Histological examinations showed different degrees of dental pulp inflammatory response and complete/incomplete dentin bridge formation during the pulp healing process at different follow-up periods. Calcium silicate materials have the ability to induce reparative dentinogenesis when applied over exposed pulps, with different behaviors, as related to the animal model used, pulpal inflammatory responses, and quality of dentin bridges.     

Combining planar and central chirality in ferrocene thiophosphine-sulfoxides

Novel chiral ferrocenylthiophosphine–sulfoxide and phosphine–sulfoxide derivatives possessing planar chirality for the ferrocene moiety and central chirality at the sulfur atom have been synthesized. These ligands can be obtained as pure diastereoisomers in both racemic and enantiomerically pure forms. Complete characterization by XRD analysis has allowed the assignment of the absolute configuration in each case. Preliminary coordination studies of the phosphine–sulfoxide ligands on platinum are also reported. These show chelating complexation by the phosphorous and sulfur atoms.     

Wastes from Wood Extraction Used in Composite Materials: Behavior after Accelerated Weathering

New materials were obtained by incorporating in polypropylene (PP) matrix 60% wood wastes resulting after extraction with supercritical carbon dioxide, water, and ethanol. Structural, mechanical, thermal, and rheological characterizations, as well as moisture uptake of the composites, were evaluated before and after accelerated weathering. It was found that the extraction method influenced the composite properties due to the hydrophilic-hydrophobic balance. The addition of extracted fibers results in an increase in hardness and tensile properties and a decrease of impact strength as compared to PP.     

Pattern Recognition of Sweeteners in Biological Fluids,Beverages, and Ketchup using Stochastic Sensors

Three stochastic sensors based on nanodiamond (nDP) paste modified with α, β, and γ‐cyclodextrin were designed and characterized for pattern recognition of aspartame, acesulfame K and sodium cyclamate in beverages, ketchup, and biological fluids. The linear concentration ranges obtained for acesulfame K (between 1.00×10^?10 mol L^?1and 1.00×10^?3 mol L^?1), for aspartame (between 1.00×10^?12 mol L^?1 and 1.00×10^?3 mol L^?1) and for sodium cyclamate (between 4.97×10^?12 mol L^?1 and 4.97×10^?3 mol L^?1) allow their assay in biological fluids, beverages and ketchup. The lowest limits of quantification were obtained using the stochastic sensor based on γ‐CD/nDP: for acesulfame K 1.00×10^?10 mol L^?1, for aspartame 1.00×10^?12 mol L^?1 and for sodium cyclamate 4.97×10^?12 mol L^?1. All three stochastic sensors revealed very high values of sensitivities. The proposed method was reliable for qualitative and quantitative assay of aspartame, acesulfame K and sodium cyclamate in beverages, ketchup, and in biological fluids such as urine.