Sensitive Electrochemical Detection of Thiabendazole in Fruits Using Ag−MoS2 Electrode

Herein, Ag nanoparticles (NPs) modified MoS₂ (Ag−MoS₂) was applied to the surface of glassy carbon (GC) to produce a robust electrochemical sensor for the detection of thiabendazole, a common antifungal in the post-harvesting of fruits. Cyclic voltammetry studies confirmed thiabendazole exhibited an irreversible, diffusion-controlled process on Ag−MoS₂ with a two-fold increase in peak current than the pristine MoS_2. A square wave voltammetry was used for the detection of TBZ. The developed sensor exhibited a linear range between 1–10 μM with LOD down to 0.1 μM (S/N>3). Analysis of TBZ in mango and banana matrices gave a recovery of 91.6–100.4 % indicating the suitability of the sensor for food safety monitoring.     

Radionuclides in biota collected near a dicalcium phosphate plant, southern Catalonia, Spain

Industrial waste containing radioactive U-decay series isotopes was released into the Ebro River, Spain, over a period of >20 years from a dicalcium phosphate (DCP) plant. This release raised activities of several natural radionuclides (e.g. ²³⁸U, ²³⁴U, ²³⁰Th, ²³²Th and ²²⁶Ra) in biota taken from the area near the DCP plant. Plants and animals selected for this study included the green algae (Cladophora glomerata), the blue mussel (Mytilus edulis), the zebra mussel (Dreissena polymorpha) and the scavenger catfish (Silurus glanis) because they are all common in the area. Multiple sampling points were chosen for this study: (1) a site in the Riba-Roja Reservoir, above the DCP plant’s area of influence, (2) four sites in the area surrounding the DCP plant, close to the town of Flix, and (3) a location in the Ebro Delta Estuary in Fangar Bay. Significant differences in the activities (in Bq kg^?1 of dry weight) for the radioisotopes included in this study among samples were attributed to sample location and the species evaluated. For instance, relatively high activities for uranium and radium were obtained in algae collected around the DCP plant, compared to results obtained for algae samples taken from the unimpacted Riba-Roja Reservoir. In contrast, for zebra mussels, enhanced activities were observed for all radionuclides and, in particular, for thorium and radium isotopes within the area of influence. Among catfish samples, activity values from different locations were not significantly different, though slightly higher activities were observed at the sampling point just downstream of the DCP factory.     

Synthesis of amphidinolide Y precursors

The Negishi coupling between a chiral C3 synthon and an iodoalkene arising from 3-butyn-1-ol, which gave the C3–C9 fragment of amphidinolide Y, was the starting point of a formal total synthesis of this marine natural product. By means of Sharpless ADH and TADDOL-mediated crotylation, the full western fragment (C1–C11) was obtained, which was coupled with the eastern fragment (3-hydroxyoxolane derivative). The penultimate step (ring-closing metathesis, with G-II, H–G-II, or Nitro-Grela reagents, under several conditions) posed great difficulties. The cyclization was achieved with 15c (7,9-bis-O-TES) and 15d (7-O-TES, 9-O-TBS); more than stoichiometric amounts of the H–G-II Ru complex were required for complete conversion.     

3β‐Acetoxy‐5α,6β‐di­hydroxybisnorcholanic acid 2216 lactone

In the title compound, C₂₄H₃₆O₆, the ester linkage in ring A is equatorial. The six‐membered rings A, B and C have chair conformations. The five‐membered ring D adopts a 13β,14α‐half‐chair conformation and the E ring adopts an envelope conformation. The A/B, B/C and C/D ring junctions are trans, whereas the D/E junction is cis.     

Time-resolved intraband electronic relaxation dynamics of Hg(n) (-) clusters (n=7-13,15,18) excited at 1.0 eV

Time-resolved photoelectron imaging has been used to study the relaxation dynamics of small Hg(n) (-) clusters (n=7-13,15,18) following intraband electronic excitation at 1250 nm (1.0 eV). This study furthers our previous investigation of single electron, intraband relaxation dynamics in Hg(n) (-) clusters at 790 nm by exploring the dynamics of smaller clusters (n=7-10), as well as those of larger clusters (n=11-13,15,18) at a lower excitation energy. We measure relaxation time scales of 2-9 ps, two to three times faster than seen previously after 790 nm excitation of Hg(n) (-), n=11-18. These results, along with size-dependent trends in the absorption cross-section and photoelectron angular distribution anisotropy, suggest significant evolution of the cluster anion electronic structure in the size range studied here. Furthermore, the smallest clusters studied here exhibit 35-45 cm(-1) oscillations in pump-probe signal at earliest temporal delays that are interpreted as early coherent nuclear motion on the excited potential energy surfaces of these clusters. Evidence for evaporation of one or two Hg atoms is seen on a time scale of tens of picoseconds.     

Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems

1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor–acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. Photo-population of the core-centred π–π* state is followed by ultrafast electron transfer from the electron donor to the NDI. Due to a solvent dependent singlet–triplet equilibrium inherent to the NDI core, both singlet and triplet charge-separated states are populated. We demonstrate that long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor–acceptor sub-units. By extending this study to a supramolecular NDI-based cage, we also show that the triplet charge-separation yield can be increased by tuning the environment.

Ultrafast electron transfer from singlet and triplet excited states in equilibrium results in the population of both singlet and triplet charge-separated states.     

Analytical fractionation of aquatic humic substances and their metal species by means of multistage ultrafiltration

The molecular-size fractionation of aquatic humic substances (HS) and their metal species by means of a novel sequential-stage ultrafiltration (UF) device equipped with five appropriate ultramembranes (1, 5, 10, 50 and 100 kD) is described. First of all, the concentration dynamics of macromolecules, particulary HS, during five-stage UF and its subsequent washing step has been modelled. Based on these results, the fractionation of aquatic HS (from ground and bog water) by means of multistage UF has been optimized for an analytical scale (10 ml sample, 1 mg/ml HS, 10 ml washing solution, pH 6.0). The molecular size-distribution of selected aquatic HS (BOC 1/2 from the DFG-Versuchsfeld Bocholt, VM 5 from Venner Moor, Germany) studied by five-stage UF exhibited strong systematic influences of the procedure used for their isolation. The molecular-size distribution of HS obtained by on-line UF and gel permeation chromatography (GPC) showed a satisfactory agreement in the range 1–50 kD. Moreover, when interrupting multistage UF for > 48 h a slow transformation in the HS samples has been found as gradually additional HS fractions of < 1 kD have been formed. Besides unloaded HS molecules, the molecular-size distribution of freshly formed metal species of HS (1.0 mg metal/g HS of Al(III), Cd(II), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), Zn(II), each) has been characterized by multistage UF as a function of pH-value, degree of loading and complexation time. Metal determinations as carried out by flame AAS, showed that considerable metal fractions in HS especially are present in molecules > 50 kD, which seemed to be rather acid-inert. With complexation times of < 2 days a transient shift of the molecular size distribution of both HS and their metal species (e.g., Al(III), Fe(III) to higher values (> 10 kD) has been found.     

Multi-component, regio-selective aldol addition of β-ketoesters to aldehydes: scope and applications

Simple and effective multi-component one-pot aldol addition/protection reactions of β-ketoesters to a series of aldehydes in the presence Me(3)SiCl and i-Pr(2)EtN have been described. The analysis of the scope of the reaction revealed a dramatic dependence of the reactivity on the substrates used. Thus the effect of a catalytic amount of DMF and different reaction conditions was widely investigated. Further transformations of the aldol adducts were particularly useful to give valuable diols and compounds with quaternary stereocenters, while X-ray structural analysis gave also important stereochemical information about this challenging reaction.     

Nitric oxide binding and photodelivery based on ruthenium(II) complexes of 4-arylazo-3,5-dimethylpyrazole

Two fluorescent ligands, 3,5-dimethyl-4-(6'-sulfonylammonium-1'-azonaphthyl)pyrazole (dmpzn, 1) and 3,5-dimethyl-4-(4'-N,N'-dimethylaminoazophenyl)pyrazole (dmpza, 2) were obtained by condensation of ketoenolic derivatives with hydrazine. 1 and 2 formed the novel dinuclear complexes [(H(2)O)(3)ClRu(micro-L)(2)RuCl(H(2)O)(3)] (3 or 4) and [(H(2)O)(NO)Cl(2)Ru(micro-L)(2)RuCl(2)(NO)(H(2)O)] (6 or 7) (where L 1 = 2 or , respectively) which were characterized by IR, NMR and elemental analysis. The nitrosyl complexes were prepared by bubbling purified nitric oxide through methanol solutions of the corresponding ruthenium(II) chloroderivative or by reaction of the appropriate ligands with Ru(NO)Cl(3). Complexes 3 and 4 were found to bind NO, resulting in an increase in fluorescence. Ligand 1 also formed the mononuclear nitrosyl complex [Ru(NO)(bpy)(2)(dmpzn)]Cl(2) (8) which released NO in water at physiological pH and in the solid state as revealed by fluorescence and IR measurements, respectively.