A field deployable method for a rapid screening analysis of inorganic arsenic in seaweed

Inorganic arsenic (iAs) in 13 store-bought edible seaweed samples and 34 dried kelp (Laminaria digitata) samples was determined by a newly developed, field-deployable method (FDM) with the aid of a field test kit for arsenic in water. Results from the FDM were compared to results from speciation analysis achieved by using high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The FDM consisted of a simple extraction method using diluted HNO₃ to quantitatively extract iAs without decomposing the organoarsenicals to iAs followed by the selective volatilisation of iAs as arsine (AsH₃) and subsequent chemo-trapping on a filter paper soaked in mercury bromide (HgBr₂) solution. Method optimization with a sub-set of samples showed 80–94% iAs recovery with the FDM with no matrix effect from organo-arsenic species in the form of dimethylarsinic acid (DMA) on the iAs concentration. The method displayed good reproducibility with an average error of ±19% and validation by HPLC-ICP-MS showed that the results from the FDM were comparable (slope = 1.03, R² = 0.70) to those from speciation analysis with no bias. The FDM can be conducted within an hour and the observed limit of quantification was around 0.05 mg kg^?1 (dry weight). This method is well suited for on-site monitoring of iAs in seaweed before it is harvested and can thus be recommended for use as a screening method for iAs in seaweed.

Open image in new window

Graphical abstract Screening seaweed for their inorganic arsenic concentration within one hour without bias has been made possible in the field by using a field deployable arsenic kit. Its accuracy and precision was compared to HPLC-ICPMS.

     

Novel flame retardants containing cyclodextrin nanosponges and phosphorus compounds to enhance EVA combustion properties

A novel flame retardant intumescent system, aimed to improve the fire stability of ethylene vinyl acetate copolymer (EVA), has been prepared by melt blending of the copolymer and a complex of cyclodextrin nanosponge-phosphorus compounds. As compared to traditional systems, this complex, stable in processing conditions, has the advantage that nanosponges act as both carbon sources and foam forming agents while the phosphorus compounds are able to directly generate phosphoric acid in situ. In this context, cyclodextrin nanosponges undergo dehydration in presence of the acid source, generating water vapour and char, and thus protecting the copolymer against combustion. Different acid sources have been investigated in order to reach the optimum interaction with the nanosponges. Raman measurements and thermogravimetric analyses have shown that the cavities of nanosponges entrapped the phosphorus derivatives forming stable complexes at the temperature of EVA processing. Different amounts of these complexes (5, 10 and 15 wt.%) have been added to EVA via melt blending and their flame retardancy properties measured by UL94 test and cone calorimetry. Strongly modified burning kinetics, as compared to the behaviour of the neat copolymer, have been found by UL94 test: V2 classification has been achieved for every formulation regardless of the type and the amount of complex used. EVA combustion behaviour by cone calorimetry has also been significantly affected: the heat release rate decreased dramatically down to ca. 20% in the presence of these new additives.     

Probing the structure, stability and hydrogen storage properties of calcium dodecahydro-closo-dodecaborate

Calcium borohydride can reversibly store up to 9.6 wt% hydrogen; however, the material displays poor cyclability, generally associated with the formation of stable intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of Ca(BH₄)₂, calcium dodecahydro-closo-dodecaborate was isolated and characterized by diffraction and spectroscopic techniques. The crystal structure of CaB₁₂H₁₂ was determined from powder XRD data and confirmed by DFT and neutron vibrational spectroscopy studies. Attempts to dehydrogenate/hydrogenate mixtures of CaB₁₂H₁₂ and CaH₂ were made under conditions known to favor partial reversibility in calcium borohydride. However, up to 670 K no notable formation of Ca(BH₄)₂ (during hydrogenation) or CaB₆ (during dehydrogenation) occurred. It was demonstrated that the stability of CaB₁₂H₁₂ can be significantly altered using CaH₂ as a destabilizing agent to favor the hydrogen release.     

Structural characterization of methanol substituted lanthanum halides

The first study into the alcohol solvation of lanthanum halide [LaX₃] derivatives as a means to lower the processing temperature for the production of the LaBr₃ scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(μ-Br)(H₂O)₇](Br)₂}₂ (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H₂O)₇(MeOH)₂](Br)₃ (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH₂, crystals of [Ca(MeOH)₆](Br)₂ (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr_2.75·5.25(MeOH)]^+0.25 [LaBr_3.25·4.75(MeOH)]^−0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr₃ in MeOH forming the 8-coordinated [LaBr₃(MeOH)₅] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX₃ derivatives were isolated as [(MeOH)₄(Cl)₂La(μ-Cl)]₂ (6) and [La(MeOH)₉](I)₃·MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (¹³⁹La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4–6 were slightly higher in comparison to their hydrated counterparts.     

Marine mammal blubber reference and control materials for use in the determination of halogenated organic compounds and fatty acids

The National Institute of Standards and Technology (NIST) has a diverse collection of control materials derived from marine mammal blubber, fat, and serum. Standard Reference Material (SRM) 1945 Organics in Whale Blubber was recertified for polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, and polybrominated diphenyl ether (PBDE) congeners. SRM 1945 has also been assigned mass fraction values for compounds not frequently determined in marine samples including toxaphene congeners, coplanar PCBs, and methoxylated PBDE congeners which are natural products. NIST also has assigned mass fraction values, as a result of interlaboratory comparison exercises, for PCB congeners, organochlorine pesticides, PBDE congeners, and fatty acids in six homogenate materials produced from marine mammal blubber or serum. The materials are available from NIST upon request; however, the supply is very limited for some of the materials. The materials include those obtained from pilot whale blubber (Homogenates III and IV), Blainville’s beaked whale blubber (Homogenate VII), polar bear fat (Homogenate VI), and California sea lion serum (Marine Mammal Control Material-1 Serum) and blubber (Homogenate V).     

Three hydrophobic amino acids in <Emphasis Type="Italic">Escherichia coli</Emphasis> HscB make the greatest contribution to the stability of the HscB-IscU complex

Background  

General iron-sulfur cluster biosynthesis proceeds through assembly of a transient cluster on IscU followed by its transfer to a recipient apo-protein. The efficiency of the second step is increased by the presence of HscA and HscB, but the reason behind this is poorly understood. To shed light on the function of HscB, we began a study on the nature of its interaction with IscU. Our work suggested that the binding site of IscU is in the C-terminal domain of HscB, and two different triple alanine substitutions ([L92A, M93A, F153A] and [E97A, E100A, E104A]) involving predicted binding site residues had detrimental effects on this interaction. However, the individual contribution of each substitution to the observed effect remains to be determined as well as the possible involvement of other residues in the proposed binding site.