Simultaneous determination of hydride (Se) and non-hydride-forming (Ca,Mg, K,P, S and Zn) elements in various beverages (beer,coffee, and milk), with minimum sample preparation,by ICP–AES and use of a dual-mode sample-introduction system

A method has been developed enabling direct analysis (i.e. after dilution only) of beer, instant coffee, milk, and milk powder by ICP–AES. Analysis of the beverages after dilution with a low concentration of HNO₃ was used for accurate determination of essential minor and trace elements (Ca, Mg, K, P, S, and Zn). Selenium, introduced as the hydride, was determined simultaneously with the other non-hydride-forming elements using the commercial multi-mode sample-introduction system (MSIS). To obtain accurate results, however, some simple pre-treatment was needed. Analysis was also performed after microwave-assisted decomposition of the samples. Three different modes of sample-preparation, i.e. dilution only, partial decomposition (aqua regia treatment), and complete decomposition were compared. The results obtained by use of the three different sample-preparation methods were in very good agreement. Results from analysis of certified reference material (SRM 1459 non-fat milk powder) also verified the accuracy of the methods. The limit of detection obtained for Se using dual-mode sample introduction was 0.5 ng mL^–1, which corresponds to approximately 2 ng g^–1 in beer and approximately 4 ng g^–1 in coffee and milk when using the recommended procedure.     

Freon (CHF<Subscript>3</Subscript>)-assisted atomization for the determination of titanium using ultrasonic slurry sampling–graphite furnace atomic absorption spectrometry (USS–GFAAS): a simple and advantageous method for solid samples

A simple and advantageous method for the determination of titanium using graphite furnace atomic absorption spectrometry with slurry sampling has been developed. Titanium is one of the refractory elements that form thermally stable carbides in the graphite tube, which leads to severe memory effects. Trifluoromethane (Freon-23) was applied in the purge gas during the atomization step or alternatively just prior to the atomization to successfully eliminate the problems of carbide formation and increase the lifetime of the furnace tube which could be used for more than 600 heating cycles. A flow rate of 40 mL min^–1 (5% of Freon in argon) was used to obtain symmetrical peaks with no tailing. However, when the gas flow rate was too high (250 mL min^–1) the peak-tailing and memory effects reappeared. Ti was determined in various materials covering a wide range of concentrations, from 2.8 g g^–1 to 12% (m/m) Ti. The accuracy of the method was confirmed by analyzing certified reference materials (CRMs) or by comparing the results with those obtained using inductively coupled plasma–atomic emission spectrometry (ICP–AES) after decomposition of the samples. The materials analyzed were soil, plant, human hair, coal, urban particulate matters, toothpaste, and powdered paint.     

Improved Synthesis of 1-Bromo-3-buten-2-one

A convenient procedure for the synthesis of 1-bromo-3-buten-2-one, 4, from commercially available 2-ethyl-2-methyl-1,3-dioxolane, 1, is described. The procedure involves three reaction steps: (1) The acetal 1 is converted to 2-(1-bromoethyl)-2-bromomethyl-1,3-dioxolane, 2, by reacting 1 with elemental bromine in dichloromethane to yield 98% of 2. (2) Dehydrobromination of 2 with potassium tert-butoxide in tetrahydrofuran gives 2-bromomethyl-2-vinyl-1,3-dioxolane, 3, in 84–93% yield. (3) Removal of the acetal protection from 3 by formolysis for 6–10 h afforded 1-bromo-3-buten-2-one, 4, in 85–94% yield. A more rapid method is acid hydrolysis of 3 under microwave activation (100 °C, 8–10 min), by which 4 was obtained in 75% yield. Full experimental details are given.

Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

A multianalytical approach to investigate stone biodeterioration at a UNESCO world heritage site: the volcanic rock-hewn churches of Lalibela, Northern Ethiopia

A multianalytical approach combining Optical Microscopy (OM), Backscattered Variable Pressure Scanning Electron Microscopy + Energy Dispersive X-ray Spectroscopy (VP-BSEM + EDS), Powder X-ray Diffractometry (PXRD), Raman Spectroscopy, and Microbiological techniques has been applied to characterize decay products and processes occurring at the surface of two rock-hewn churches (Bete Gyorgis and Bete Amanuel) at the UNESCO’s World Heritage site of Lalibela, Northern Ethiopia. The two churches were carved into volcanic scoria deposits of basaltic composition. In their geological history, the Lalibela volcanic rocks underwent late to post-magmatic hydrothermal alteration together with partial laterization and are therefore characterized by a decay-prone highly vesicular microtexture with late stage to post-magmatic precipitation of secondary mineral phases (calcite–zeolite–smectite). The main objective of the study was to gain a better insight into the weathering products and mechanisms affecting the surface of the stone monuments and to assess the relative contribution of natural “geological” weathering processes versus biological/salt attack in stone decay at this unique heritage site. Results indicate that while the main cause of bulk rock deterioration and structural failure could be related to the stone inherited “geological” features, biological attack by micro- (bacteria) and/or macro- (lichens) organisms is currently responsible for severe stone surface physical and chemical weathering leading to significant weakening of the stone texture and to material loss at the surface of the churches walls. A prompt and careful removal of the biological patinas with the correct biocidal treatment is therefore recommended.     

Overview of sample introduction techniques prior to GC for the analysis of volatiles in solid materials

Sample preparation and introduction techniques are very critical steps in gas chromatography analysis and particularly in the analysis of volatiles in solid samples. In these cases, they can be divided into two main categories: direct and indirect approaches, based on how the solid sample is treated, i.e. with and without dissolution (or extraction) of analytes from the solid sample. To enable routine application, coupling with sample preparation techniques (especially solid or solvent‐based microextractions) is needed to achieve automation. Here, an overview of the most common sample introduction techniques for gas chromatography with their advantages and drawbacks is presented and discussed, including references to relevant examples. So, this review can serve as guidance for new users.     

Thermodynamics of peptide insertion and aggregation in a lipid bilayer

A variety of biomolecules mediate physiological processes by inserting and reorganizing in cell membranes, and the thermodynamic forces responsible for their partitioning are of great interest. Recent experiments provided valuable data on the free energy changes associated with the transfer of individual amino acids from water to membrane. However, a complete picture of the pathways and the associated changes in energy of peptide insertion into a membrane remains elusive. To this end, computational techniques supplement the experimental data with atomic-level details and shed light on the energetics of insertion. Here, we employed the technique of umbrella sampling in a total 850 ns of all-atom molecular dynamics simulations to study the free energy profile and the pathway of insertion of a model hexapeptide consisting of a tryptophan and five leucines (WL5). The computed free energy profile of the peptide as it travels from bulk solvent through the membrane core exhibits two minima: a local minimum at the water-membrane interface or the headgroup region and a global minimum at the hydrophobic-hydrophilic interface close to the lipid glycerol region. A rather small barrier of roughly 1 kcal mol (-1) exists at the membrane core, which is explained by the enhanced flexibility of the peptide when deeply inserted. Combining our results with those in the literature, we present a thermodynamic model for peptide insertion and aggregation which involves peptide aggregation upon contact with the membrane at the solvent-lipid headgroup interface.     

H-ras protein in a bilayer: interaction and structure perturbation

Ras GTPases become functionally active when anchored to membranes by inserting their lipid modified side chains. Their role in cell division, development, and cancer has made them targets of extensive research efforts, yet the mechanism of membrane insertion and the structure of the resulting complex remain elusive. Recently, the structure of the full-length H-ras protein in a DMPC bilayer has been computationally characterized. Here, the atomic interactions between the H-ras membrane anchor and the DMPC bilayer are investigated in detail. We find that the palmitoylated cysteines and Met182 have dual contributions to membrane affinity: hydrogen bonding by their amides and van der Waals interaction by their hydrophobic side chains. The polar side chains help maintain the orientation of the anchor. Although the overall structure of the bilayer is similar to that of a pure DMPC, there are localized perturbations. These perturbations depend on the insertion depth and backbone localization of the anchor, which in turn is modulated by the catalytic domain and the linker. The pattern of anchor amide-DMPC phosphate/carbonyl hydrogen bonds and the flexibility of Palm184 are important in discriminating between different modes of ras-DMPC interactions. The results provide structural arguments in support of the proposed participation of ras in the organization of membrane nanoclusters.