Characterization of Iron Sulfide Species in Model Solutions by Cyclic Voltammetry. Revisiting an Old Problem

A long‐standing problem associated with voltammetric determination of iron and sulfide in reduced natural waters has been the nature of the presumed analyte responsible for a reduction peak at ?1.1 V vs. Ag/AgCl. Cyclic voltammetry at the Hg electrode is used here to study solutions with different Fe(II) to sulfide ratios in chloride and acetate electrolytes (pH 6–7). The results indicate that the ?1.1 V peak can be assigned to reduction of Fe²⁺ or its labile complexes on FeS layers that partially cover the Hg electrode. Hg electrodes covered with FeS act like FeS solid electrodes over a very wide potential range (?0.35 to ?1.9 V). Two mechanisms for forming FeS layers on Hg are described. Over the broadest deposition potential range, the dominant mechanism involves attachment at the Hg surface of FeS nanoparticles, which are generated quickly in initially supersaturated mixtures of Fe(II) and S(–II). In a narrow deposition potential range, roughly ?0.56 to ?0.70, FeS layers are produced additionally by replacement of preformed HgS. Because Fe²⁺ is reduced at ?1.1 V on FeS layers and at ?1.4 V on bare Hg, it may be underdetermined when only the ?1.4 V peak is measured.     

Bioaccumulative and conchological assessment of heavy metal transfer in a soil-plant-snail food chain

ABSTRACT: BACKGROUND: Copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb) can pose serious threats to environmental health because they tend to bioaccumulate in terrestrial ecosystems. We investigated under field conditions the transfer of these heavy metals in a soil-plant-snail food chain in Banat area, Romania. The main goal of this paper was to assess the Roman snail (Helix pomatia) usefulness in environmental monitoring as bioindicator of heavy metal accumulation. Eight sampling sites, selected by different history of heavy metal (HM) exposure, were chosen to be sampled for soil, nettle leaves, and newly matured snails. This study also aimed to identify the putative effects of HM accumulation in the environment on phenotypic variability in selected shell features, which included shell height (SH), relative shell height (RSH), and whorl number (WN). RESULTS: Significantly higher amounts of HMs were accumulated in snail hepatopancreas and not in foot. Cu, Zn, and Cd have biomagnified in the snail body, particularly in the hepatopancreas. In contrast, Pb decreased when going up into the food chain. Zn, Cd, and Pb correlated highly with each other at all levels of the investigated food chain. Zn and Pb exhibited an effective soil-plant transfer, whereas in the snail body only foot Cu concentration was correlated with that in soil. There were significant differences among sampling sites for WN, SH, and RSH when compared with reference snails. WN was strongly correlated with Cd and Pb concentrations in nettle leaves but not with Cu and Zn. SH was independent of HM concentrations in soil, snail hepatopancreas, and foot. However, SH correlated negatively with nettle leaves concentrations for each HM except Cu. In contrast, RSH correlated significantly only with Pb concentration in hepatopancreas. CONCLUSIONS: The snail hepatopancreas accumulates high amounts of HMs, and therefore, this organ can function as a reliable biomarker for tracking HM bioavailability in soil. Long-term exposure to HMs via contaminated food might influence the variability of shell traits in snail populations. Therefore, our results highlight the Roman snail (Helix pomatia) potential to be used in environmental monitoring studies as bioindicator of HM pollution.     

Ultrafast Energy Transfer in Triptycene‐Grafted Bodipy Scaffoldings

A series of new compounds in which various Bodipy dyes are grafted logically on triptycene rigid structures are synthesized and characterized, and their absorption spectra and photophysical properties are studied, also by pump‐probe transient absorption spectroscopy. The studied compounds are: the mono‐Bodipy species TA, TB, and TC (where A, B, and C identify different Bodipy subunits absorbing and emitting at different wavelengths), the multichromophore species TA₃, which bears three identical A subunits, and the three multichromophoric species TAB, TBC, and TABC, all of them containing at least two different types of Bodipy subunits. The triptycene moiety plays the role of a rigid scaffold, keeping the various dyes at predetermined distances and allowing for a three‐dimensional structural arrangement of the multichromophoric species. The absorption spectra of the multichromophoric Bodipy species are essentially additive, indicating that negligible inter‐chromophoric interaction takes place at the ground state. Luminescence properties and transient absorption spectroscopy indicate that a very fast (on the picosecond time scale) and efficient photoinduced energy transfer occurs in all the multi‐Bodipy species, with the lower‐energy Bodipy subunits of each multi‐Bodipy compounds playing the role of an electronic energy collector. In TAB, an energy transfer from the A‐type Bodipy subunit to the B‐type one takes place with a rate constant of 1.6×10¹⁰ s^?1, whereas in TBC an energy transfer from the B‐type Bodipy subunit to the C‐type subunit is bi‐exponential, exhibiting rate constants of 1.7×10¹¹ and 1.9×10¹⁰ s^?1; the possible presence of different conformers with different donor–acceptor distances in this bichromophoric species is proposed to cause the bi‐exponential energy‐transfer process. Interpretation of the intricate energy‐transfer pathways occurring in TABC is made with the help of the processes identified in the bichromophoric compounds. In all cases, the measured energy‐transfer rate constants agree with a Förster mechanism for the energy‐transfer processes.     

Dimension estimation in sufficient dimension reduction: A unifying approach

Sufficient Dimension Reduction (SDR) in regression comprises the estimation of the dimension of the smallest (central) dimension reduction subspace and its basis elements. For SDR methods based on a kernel matrix, such as SIR and SAVE, the dimension estimation is equivalent to the estimation of the rank of a random matrix which is the sample based estimate of the kernel. A test for the rank of a random matrix amounts to testing how many of its eigen or singular values are equal to zero. We propose two tests based on the smallest eigen or singular values of the estimated matrix: an asymptotic weighted chi-square test and a Wald-type asymptotic chi-square test. We also provide an asymptotic chi-square test for assessing whether elements of the left singular vectors of the random matrix are zero. These methods together constitute a unified approach for all SDR methods based on a kernel matrix that covers estimation of the central subspace and its dimension, as well as assessment of variable contribution to the lower-dimensional predictor projections with variable selection, a special case. A small power simulation study shows that the proposed and existing tests, specific to each SDR method, perform similarly with respect to power and achievement of the nominal level. Also, the importance of the choice of the number of slices as a tuning parameter is further exhibited.     

Nonequilibrium States in HTS Tapes under the Action of Short Current Pulses

This paper presents the results of studying the nonequilibrium processes in second generation HTS tapes under the action of pulsed current loads. In the study, we used short current pulses of various amplitudes from 0.9 to 5 values of the superconductor critical current. The minimum rise time of the current was 8 µs, and the pulse duration was from 1 to 250 µs. Comparisons in the behavior of samples under long current pulses with current rise time more than 3 ms were carried out. A qualitative difference in the formation of an nonequilibrium state during short and long current pulses was found. A stable current flow with amplitudes up to 4 times larger than the critical current was obtained without degradation of the superconductor. Experimental results were analyzed on the basis of the dynamic resistance model in the flux flow regime.     

Design, synthesis and redox properties of a fluorene platform linking two different Bodipy dyes

Several new fluorophores have been prepared by grafting boradiazaindacene (red absorbing) and/or styrylboradiazaindacene (blue absorbing) units as terminal energy acceptors onto a fluorene-derived platform. In one case, an amino-bis(bipyridine) pocket has been attached to enable strong binding of transition metal ions. The stepwise syntheses were largely based on Pd-catalysed cross-coupling reactions. The electrochemistry of the dyes has been analysed by reference to the properties of the various synthetic intermediates, protonation of the tertiary amine site present in the bis(bipyridine) species enabling processes involving this centre to be distinguished from those associated with the boradiazaindacene (Bodipy) unit.     

Loop homology of bi-secondary structures II

Journal of Algebraic Combinatorics - In this paper, we analyze the homology of the simplicial complex induced by a given pair of RNA secondary structures, $$R=(S,T)$$ . Such a pair induces a...     

Absorption tuning of monosubstituted triazatruxenes for bulk heterojunction solar cells

A series of triazatruxene (TAT)-functionalized Bodipy dyes were prepared by a sequence of reactions involving either cross-coupling reactions promoted by Pd complexes or a Knoevenagel reaction leading to a vinyl linker. The new dyes show large absorption coefficients and fluorescence quantum yields as well as interesting electrochemical properties. The blue dyes of this series exhibit interesting photovoltaic effects (V(OC) = 0.83 V, J(SC) = 3.6 mA/cm(2), efficiency 0.9%) in bulk heterojunction solar cells, due to the good hole mobility imported by the TAT entity.