Sequential hydride generation/pneumatic nebulisation inductively coupled plasma mass spectrometry for the fractionation of arsenic and selenium species

The toxicity of certain elements is known to be related to their organic substituents and/or oxidation states. As such, total elemental determinations do not always yield sufficient information for accurate risk assessments and therefore speciation or fractionation data are required. In order to obtain fractionation data for trace levels of arsenic and selenium, a novel sequential pneumatic nebulisation (PN)/hydride generation (HG) inductively coupled plasma mass spectrometry (ICP-MS) method was developed. The method offers the advantage of sample introduction via either PN or HG by simply rotating a 4-way switching valve while the system is in operation. In PN mode, the liquid sample is aspirated into ICP, allowing for the determination of the total amount of each element, whilst in HG mode only the arsenic and selenium species that form volatile hydrides are determined. Conveniently, in the case of arsenic, this allows for differentiation between the four most toxic arsenic species (arsenate, arsenite, monomethylarsonic acid and dimethylarsinic acid), which form volatile hydrides, and the virtually non-toxic forms (arsenobetaine, arsenosugars, etc.), which do not. This allows for the rapid estimation of the amounts of toxic and non-toxic arsenic species present in a sample. For arsenic, the technique gave detection limits of 36 ng l⁻¹ in PN mode and 1 ng l⁻¹ in HG mode. For selenium, detection limits of 150 ng l⁻¹ were achieved in PN mode and 220 ng l⁻¹ in HG mode. The technique also gave good long- and short-term stabilities of under 6% RSD for both elements. A variety of samples, including water and urine standard reference materials, were analysed in both modes, and the precision and accuracy of the results for total arsenic and selenium levels were assessed. Using the technique in both modes also allowed for the fractionation of As and Se species into their volatile hydride-forming and non-hydride-forming species. This was particularly informative, with respect to As species present, in the case of a kelp powder extract. Digested tobacco samples were only analysed for their total As levels, in which case results obtained via both sample introduction modes showed good agreement.     

Ionothermal Synthesis of Triazine–Heptazine‐Based Copolymers with Apparent Quantum Yields of 60 % at 420 nm for Solar Hydrogen Production from “Sea Water”

Polymeric carbon nitride (PCN), in either triazine or heptazine form, has been regarded as a promising metal‐free, environmentally benign, and sustainable photocatalyst for solar hydrogen production. However, PCN in most cases only exhibits moderate activity owing to its inherent properties, such as rapid charge carrier recombination. Herein we present a triazine–heptazine copolymer synthesized by simple post‐calcination of PCN in eutectic salts, that is, NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of an internal triazine–heptazine donor–acceptor (D‐A) heterostructure was affirmed to significantly accelerate interface charge transfer (CT) and thus boost the photocatalytic activity (AQY=60 % at 420 nm). This study highlights the construction of intermolecular D‐A copolymers in NaCl/KCl molten salts with higher melting points but in the absence of lithium to modulate the chemical structure and properties of PCN.     

A hereditarily indecomposable $ {\mathcal{L}_{\infty}} $-space that solves the scalar-plus-compact problem

We construct a hereditarily indecomposable Banach space with dual space isomorphic to ℓ ₁. Every bounded linear operator on this space is expressible as λI + K, with λ a scalar and K compact.     

Mass spectrometric identification and characterization of antimony complexes with ribose-containing biomolecules and an RNA oligomer

Mass spectrometric techniques have been used to study the interaction of inorganic Sb(V) with biomolecules containing a ribose or deoxyribose moiety. Electrospray (ES) mass spectra of reaction mixtures containing inorganic Sb(V) and one of several biomolecules (adenosine, cytidine, guanosine, uridine, adenosine-5′-monophosphate, adenosine-3′,5′-cyclic monophosphate, ribose, or 2′-deoxyadenosine) afforded high-mass antimony-containing ions corresponding to Sb(V)–biomolecule complexes of stoichiometry 1:1, 1:2, or 1:3. The complexes were characterized by collision-induced dissociation (CID) tandem mass spectrometry (MS) using ion-trap multistage MS. The CID results revealed that Sb(V) binds to the ribose or deoxyribose moiety. Structures are proposed for the Sb–biomolecule complexes. Analysis of the reaction mixtures by reversed-phase chromatography coupled on-line to either inductively coupled plasma (ICP) MS or ES–MS showed that in solution Sb(V) forms complexes with all the analyzed biomolecules with vicinal cis hydroxyl groups. Evidence (from size-exclusion chromatography ICP–MS and direct infusion ES–MS) of complexation of Sb(V) with an RNA oligomer, but not with a DNA oligomer, supports the suggestion that the presence of vicinal cis hydroxyl groups is critical for complexation to occur. This is the first direct evidence of complexation of Sb(V) with RNA. Results obtained by studying the effect of changing reaction conditions, i.e. pH, reaction time, and Sb/biomolecule molar ratio, on the extent of Sb–biomolecule formation suggest the reaction may be of physiological importance. Selected reaction monitoring (SRM) and precursor-ion-scanning tandem MS were investigated to determine their potential to detect trace levels of the Sb–biomolecule complexes in biological samples. Application of SRM MS–MS in combination with high-performance liquid chromatography enabled successful detection of an Sb–adenosine complex that had been spiked into a complex biological matrix (liver homogenate).Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Identification of the novel thio-arsenosugars DMThioAsSugarCarboxyl, DMThioAsSugarCarbamate and DMThioAsSugarAdenine in extracts of giant clam tissues by high-performance liquid chromatography online with electrospray tandem mass spectrometry

Recently, the identification of four thio-arsenosugars in extracts of marine samples was reported. The biosynthesis of these arsenic species is most likely closely related to the well known oxo-arsenosugars. Due to their symbiotic algae giant clams contain oxo-arsenosugars with Carboxyl-, Carbamate- and Adenine-aglycone in significant amounts. Now we provide evidence for the presence of the thio analogues of these three arsenosugars in tissue extracts of the giant clams Tridacna maxima and Tridacna derasa. Anion-exchange high-performance liquid chromatography (HPLC) online with electrospray tandem mass spectrometry was applied for the identification of the thio-arsenosugars and the indirect quantification via their oxo analogues.     

High‐density polyethylene layered silicate nanocomposites: Effect of mechanical stretching on the crystal‐to‐crystal transformations,morphology, and extent of exfoliation

High‐density polyethylene/clay nanocomposites were elongated until breakage to investigate the effect of the mechanical stretching on the crystal‐to‐crystal transformations and their morphology. Crystalline transformations of the polymer matrix were studied via Fourier transform infrared spectroscopy, differential scanning calorimetry, and X‐ray diffraction measurements. It was concluded that the stress‐induced crystal‐to‐crystal transformations from orthorhombic structures to monoclinic and pseudohexagonal structures as well as the back‐transformation during relaxation were hindered by the presence of the clay. X‐ray diffraction studies on stretched samples showed that the mechanical stretching led from an intercalated structure to an almost exfoliated structure. These findings agreed with scanning electron micrographs, in which the beneficial effect of stretching on the exfoliation of the clay was evident. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 914–924, 2006     

Characterization of changes induced by ageing to the microstructure of pure cellulose paper by use of a gravimetric water vapour adsorption technique

The changes induced to paper microstructure by accelerated ageing were studied using an automated gravimetric technique based on water vapour adsorption. The technique can be used especially in applications involving the adsorption and desorption of water, such as paper recycling, hornification, ageing and aqueous conservation treatments. The logistics for the calculation of the specific surface area of the examined samples are presented, and the f-plot technique was applied for the visualization and interpretation of the results. These indicated that ageing reduced the adsorption and the swelling capacity of the paper, resulting in a more compact structure, increasing crystallinity and promoting hornification.     

Non-dentable sets in Banach spaces with separable dual

A non-RNP Banach spaceE is constructed such thatE ^* is separable and the RNP is equivalent to the PCP on the subsets ofE.     

A universal building block for the approximate analysis of a shared buffer ATM switch architecture

A universal analytic approximation is proposed for the performance analysis of a general queueing model of a shared buffer ATM switch architecture with bursty arrivals. The forms of the joint, aggregate and marginal state probabilities are characterised via entropy maximisation. As an application, a continuous-time maximum entropy (ME) solution is implemented at equilibrium by assuming that the arrival process to each port of the ATM switch is modelled by a Compound Poisson Process (CPP) with geometrically distributed batches. Consequently, efficientz-transform-type recursive expressions of low computational cost are derived. Validation tests against simulation show that the ME approximation is credible with a very good error-level. Moreover, performance bounds for the mean queue length and cell-loss probability at each output port are experimentally defined over those generated by Interrupted Poisson Processes (IPPs) having the same first two interarrival-time moments.This work is sponsored by the Science and Engineering Research Council (SERC), UK, under grants GR/F 29271 and GR/H 18609.     

Hereditarily indecomposable Banach algebras of diagonal operators

We provide a characterization of the Banach spaces X with a Schauder basis (e _n ) _n∈ℕ which have the property that the dual space X* is naturally isomorphic to the space L _diag(X) of diagonal operators with respect to (e _n ) _n∈ℕ. We also construct a Hereditarily Indecomposable Banach space $ \mathfrak{X} $ \mathfrak{X} _D with a Schauder basis (e _n ) _n∈ℕ such that $ \mathfrak{X} $ \mathfrak{X} *_D is isometric to L _diag($ \mathfrak{X} $ \mathfrak{X} _D) with these Banach algebras being Hereditarily Indecomposable. Finally, we show that every T ∈ L _diag($ \mathfrak{X} $ \mathfrak{X} _D) is of the form T = λI + K, where K is a compact operator.