Slurry sampling for determination of lead in marine plankton by electrothermal atomic absorption spectrometry

A slurry sampling method has been developed for the determination of Pb in marine plankton by ETAAS using a freshwater plankton certified reference material (CRM 414). Slurries were prepared in 1–3% m/v range with 1% v/v HNO₃ by ultrasonic agitation for 5 min. The effects of several chemical modifiers, including Ir(NO₃)₂, Mg(NO₃)₂, Pd(NO₃)₂, Pd(NO₃)₂ + Mg(NO₃)₂, and Mg(NO₃)₂ + NH₄H₂PO₄, were investigated for the stabilization of Pb during thermal pretreatment. Lead in slurries was effectively stabilized up to 1000 °C with Ir, Pd and Pd + Mg modifiers among which Pd + Mg provided the best results with complete atomization at 1850 °C. Firings in the presence of Ir were, problematic due to ash formation inside the atomizer. Water, dilute HNO₃ and HF were examined as suspension medium. Dilute HNO₃ (1–2% v/v) proved to be advantageous over water as it afforded extraction of Pb from plankton almost quantitatively in 5 min agitation. Hydrofluoric acid was the least suitable medium. Increasing HF concentration up to 5% v/v resulted in inaccuracy and substantial background absorption. Fast-heating furnace method provided comparable accuracy and precision to that of conventional-heating in slurries of CRM 414. Detection limits and characteristic masses were, respectively, 0.49 μg L^− 1 and 32 pg for the conventional method and 0.62 μg L^− 1 and 37 pg for the fast-heating method. However, fast-heating approach suffered from distorted peaks at high temperatures and incomplete pyrolysis of matrix at lower temperatures. Analysis of marine plankton samples for Pb was performed by using the conventional furnace program. The results showed a high correlation with those obtained by solution ICP-MS. Differences were statistically insignificant within 95% confidence interval.     

Si-E (E = N, O, F) bonding in a hexacoordinated silicon complex: new facts from experimental and theoretical charge density studies

The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment.     

Chromatographic speciation of anionic and neutral selenium compounds in Se-accumulating Brassica juncea (Indian mustard) and in selenized yeast

Selenium-accumulating plants such as Brassica juncea (Indian mustard) concentrate the element in plant shoots and roots. Such behavior may provide a cost-effective technology to clean up contaminated soils and waters that pose major environmental and human health problems (phytoremediation). Such ability to transform selenium into bioactive compounds has important implications for human nutrition and health. Element selective characterization of B. juncea grown in the presence of inorganic selenium under hydroponic conditions provides valuable information to better understand selenium metabolism in plants. The present work determines both previously observed organoselenium species such as selenomethionine and Se-methylselenocysteine and for the first time detects the newly characterized S-(methylseleno)cysteine in plant shoots and roots when grown in the presence of selenate or selenite as the only selenium source. A key feature of this study is the complementary role of selenium and sulfur specific chromatographic detection by HPLC with interfaced inductively coupled plasma mass spectrometry (ICP-MS) detection and by derivatization GC with interfaced atomic spectral emission. HPLC-ICP-MS limits of detection for such species were in the range 5-50 ng Se mL(-1) in the injected extracts. Speciation profiles are compared with those of selenium-enriched yeast by both HPLC-ICP-MS and GC-AED.     

Synthesis of 1,2,3-triarylpyrroles from 1-benzylbenzotriazoles via [1 + 2 + 2] annulation

1,2,3-Triarylpyrroles 7 have been synthesized by sequential lithiation and alkylation of 1-benzylbenzo-triazoles 1 with 2-bromoacetaldehyde diethyl acetal (2) and N-benzylideneaniline (4), followed by treatment with formic acid in ethanol.     

What is (Correct) Practical Reasoning?

This paper argues that practical reasoning is a mental process which leads a person from a set of existent mental states to an intention. In Section 1, I defend this view against two other proposals according to which practical reasoning either concludes in an action itself or in a normative belief. Section 2 discusses the correctness of practical reasoning and explains how the correctness of instrumental reasoning can be explained by the logical relations that hold between the contents of the mental states. In Section 3, I explore the correctness of normative practical reasoning. I conclude with the sceptical view that correct practical reasoning cannot require us to intend to do what we believe we ought to do.     

Engineering a Small HOMO–LUMO Gap and Intramolecular C−H Borylation by Diborene/Anthracene Orbital Intercalation

The diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) ( 6 ) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their π(C₁₄) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO–LUMO gap (HLG) and ultimately a C−H borylation of the anthryl unit. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV/Vis absorption spectrum (THF, λ_onset=788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B−B and C¹−H bonds of 8 were cleaved to give the cyclic 1,9-diborylanthracene 9 .     

Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.     

Tuning the Product Spectrum of a Glycoside Hydrolase Enzyme by a Combination of Site-Directed Mutagenesis and Tyrosine-Specific Chemical Modification

Selective chemical modification of proteins plays a pivotal role for the rational design of enzymes with novel and specific functionalities. In this study, a strategic combination of genetic and chemical engineering paves the way for systematic construction of biocatalysts by tuning the product spectrum of a levansucrase from Bacillus megaterium (Bm-LS), which typically produces small levan-like oligosaccharides. The implementation of site-directed mutagenesis followed by a tyrosine-specific modification enabled control of the product synthesis: depending on the position, the modification provoked either enrichment of short oligosaccharides (up to 800 % in some cases) or triggered the formation of high molecular weight polymer. The chemical modification can recover polymerization ability in variants with defective oligosaccharide binding motifs. Molecular dynamic (MD) simulations provided insights into the effect of modifying non-native tyrosine residues on product specificity.