Dynamic high-resolution computer simulation of electrophoretic enantiomer separations with neutral cyclodextrins as chiral selectors.

GENTRANS, a comprehensive one-dimensional dynamic simulator for electrophoretic separations and transport, was extended for handling electrokinetic chiral separations with a neutral ligand. The code can be employed to study the 1:1 interaction of monovalent weak and strong acids and bases with a single monovalent weak or strong acid or base additive, including a neutral cyclodextrin, under real experimental conditions. It is a tool to investigate the dynamics of chiral separations and to provide insight into the buffer systems used in chiral capillary zone electrophoresis (CZE) and chiral isotachophoresis. Analyte stacking across conductivity and buffer additive gradients, changes of additive concentration, buffer component concentration, pH, and conductivity across migrating sample zones and peaks, and the formation and migration of system peaks can thereby be investigated in a hitherto inaccessible way. For model systems with charged weak bases and neutral modified β-cyclodextrins at acidic pH, for which complexation constants, ionic mobilities, and mobilities of selector-analyte complexes have been determined by CZE, simulated and experimentally determined electropherograms and isotachopherograms are shown to be in good agreement. Simulation data reveal that CZE separations of cationic enantiomers performed in phosphate buffers at low pH occur behind a fast cationic migrating system peak that has a small impact on the buffer composition under which enantiomeric separation takes place.

Daytime Low Stratiform Cloud Detection on AVHRR Imagery

The near-real time retrieval of low stratiform cloud (LSC) coverage is of vital interest for such disciplines as meteorology, transport safety, economy and air quality. Within this scope, a novel methodology is proposed which provides the LSC occurrence probability estimates for a satellite scene. The algorithm is suited for the 1 × 1 km Advanced Very High Resolution Radiometer (AVHRR) data and was trained and validated against collocated SYNOP observations. Utilisation of these two combined data sources requires a formulation of constraints in order to discriminate cases where the LSC is overlaid by higher clouds. The LSC classification process is based on six features which are first converted to the integer form by step functions and combined by means of bitwise operations. Consequently, a set of values reflecting a unique combination of those features is derived which is further employed to extract the LSC occurrence probability estimates from the precomputed look-up vectors (LUV). Although the validation analyses confirmed good performance of the algorithm, some inevitable misclassification with other optically thick clouds were reported. Moreover, the comparison against Polar Platform System (PPS) cloud-type product revealed superior classification accuracy. From the temporal perspective, the acquired results reported a presence of diurnal and annual LSC probability cycles over Europe.

Direct observation of liquid crystals using cryo-TEM: Specimen preparation and low-dose imaging

Liquid crystals (LCs) represent a challenging group of materials for direct transmission electron microscopy (TEM) studies due to the complications in specimen preparation and the severe radiation damage. In this paper, we summarize a series of specimen preparation methods, including thin film and cryo-sectioning approaches, as a comprehensive toolset enabling high-resolution direct cryo-TEM observation of a broad range of LCs. We also present comparative analysis using cryo-TEM and replica freeze-fracture TEM on both thermotropic and lyotropic LCs. In addition to the revisits of previous practices, some new concepts are introduced, e.g., suspended thermotropic LC thin films, combined high-pressure freezing and cryo-sectioning of lyotropic LCs, and the complementary applications of direct TEM and indirect replica TEM techniques. The significance of subnanometer resolution cryo-TEM observation is demonstrated in a few important issues in LC studies, including providing direct evidences for the existence of nanoscale smectic domains in nematic bent-core thermotropic LCs, comprehensive understanding of the twist-bend nematic phase, and probing the packing of columnar aggregates in lyotropic chromonic LCs. Direct TEM observation opens ways to a variety of TEM techniques, suggesting that TEM (replica, cryo, and in situ techniques), in general, may be a promising part of the solution to the lack of effective structural probe at the molecular scale in LC studies. Microsc. Res. Tech. 77:754-772, 2014. © 2014 Wiley Periodicals, Inc.

1H HR-MAS NMR Based Metabolic Profiling of Cells in Response to Treatment with a Hexacationic Ruthenium Metallaprism as Potential Anticancer Drug.

1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy was applied in combination with multivariate statistical analyses to study the metabolic response of whole cells to the treatment with a hexacationic ruthenium metallaprism [1]6+ as potential anticancer drug. Human ovarian cancer cells (A2780), the corresponding cisplatin resistant cells (A2780cisR), and human embryonic kidney cells (HEK-293) were each incubated for 24 h and 72 h with [1]6+ and compared to untreated cells. Different responses were obtained depending on the cell type and incubation time. Most pronounced changes were found for lipids, choline containing compounds, glutamate and glutathione, nucleotide sugars, lactate, and some amino acids. Possible contributions of these metabolites to physiologic processes are discussed. The time-dependent metabolic response patterns suggest that A2780 cells on one hand and HEK-293 cells and A2780cisR cells on the other hand may follow different cell death pathways and exist in different temporal stages thereof.

Toward Cove-Edged Low Band Gap Graphene Nanoribbons

Graphene nanoribbons (GNRs), defined as nanometer-wide strips of graphene, have attracted increasing attention as promising candidates for next-generation semiconductors. Here, we demonstrate a bottom-up strategy toward novel low band gap GNRs (E-g = 1.70 eV) with a well-defined cove-type periphery both in solution and on a solid substrate surface with chrysene as the key monomer. Corresponding cyclized chrysene-based oligornerS consisting of the dimer and tetramer are obtained via an Ullmann Coupling followed by oxidative intramolecular cyclodehydrogenation in solution, and much higher GNR homologues via on-surface synthesis. These oligomers adopt nonplanar structures due to the isteric repulsion between the two C-H bonds at the inner cove position. Characterizations by single crystal X-ray analysis, UV-vis absorption spectroscopy, NMR spectroscopy, and scanning tunneling microscopy (STM) are described. The interpretation is assisted by density functional theory (DFT) calculations.

Late-Holocene climate variability and ecosystem responses in Alaska inferred from high-resolution multiproxy sediment analyses at Grizzly Lake

The late-Holocene shift from Picea glauca (white spruce) to Picea mariana (black spruce) forests marked the establishment of modern boreal forests in Alaska. To understand the patterns and drivers of this vegetational change and the associated late-Holocene environmental dynamics, we analyzed radiocarbon-dated sediments from Grizzly Lake for chironomids, diatoms, pollen, macrofossils, charcoal, element composition, particle size, and magnetic properties for the period 4100–1800 cal BP. Chironomid assemblages reveal two episodes of decreased July temperature, at ca. 3300–3150 (ca −1 °C) and 2900–2550 cal BP (ca −2 °C). These episodes coincided with climate change elsewhere in the Northern Hemisphere, atmospheric reorganization, and low solar activity. Diatom-inferred lake levels dropped by ca. 5 m at 3200 cal BP, suggesting dry conditions during the period 3200–1800 cal BP. P. glauca declined and P. mariana expanded at ca. 3200 cal BP; this vegetational change was linked to diatom-inferred low lake levels and thus decreased moisture availability. Forest cover declined at 3300–3100, 2800–2500 and 2300–2100 cal BP and soil erosion as inferred from increased values of Al, K, Si, Ti, and Ca intensified, when solar irradiance was low. Plant taxa adapted to disturbance and cold climate (e.g. Alnus viridis, shrub Betula, Epilobium) expanded during these periods of reduced forest cover. This open vegetation type was associated with high fire activity that peaked at 2800 cal BP, when climatic conditions were particularly cold and dry. Forest recovery lagged behind subsequent climate warming (≤+3 °C) by ca. 75–225 years. Our multiproxy data set suggests that P. glauca was dominant under warm-moist climatic conditions, whereas P. mariana prevailed under cold-dry and warm-dry conditions. This pattern implies that climatic warming, as anticipated for this century, may promote P. glauca expansions, if moisture availability will be sufficiently high, while P. mariana may expand under dry conditions, possibly exacerbating climate impacts on the fire regime.

Search for Low-Molecular-Weight Biomarkers in Plant Tissues and Seeds Using Metabolomics: Tools, Strategies, and Applications

This chapter summarises the metabolomic strategies currently in force used in plant science and describes the methods used. The metabolite profiling and fingerprinting of plant tissues through MS- and/or NMR-based approaches and the subsequent identification of biomarkers is detailed. Strategies for the microisolation and de novo identification of unknown biomarkers are also discussed. The various approaches are illustrated by a metabolomic study of the maize response to herbivory. A review of recent metabolomic studies performed on seed and crop plant tissues involving various analytical strategies is provided.

Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets

The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and density functional theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on quantum theory of atoms in molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers.

A Multiplex Real-Time PCR with High Resolution Melting Analysis for the Characterization of Antimicrobial Resistance in Neisseria gonorrhoeae.

Resistance to antibiotics used against Neisseria gonorrhoeae infections is a major public health concern. Antimicrobial resistance (AMR) testing relies on time-consuming culture-based methods. Development of rapid molecular tests for detecting AMR determinants could provide valuable tools for surveillance, epidemiological studies and to inform individual case management. We developed a fast (<1.5 hrs) SYBR-green based real-time PCR method with high resolution melting (HRM) analysis. One triplex and three duplex reactions included two sequences for N. gonorrhoeae identification and seven determinants of resistance to extended-spectrum cephalosporins (ESCs), azithromycin, ciprofloxacin, and spectinomycin. The method was validated by testing 39 previously fully-characterized N. gonorrhoeae strains, 19 commensal Neisseria spp., and an additional panel of 193 gonococcal isolates. Results were compared with culture-based AMR determination. The assay correctly identified N. gonorrhoeae and the presence or absence of the seven AMR determinants. There was some cross-reactivity with non-gonococcal Neisseria species and the detection limit was 10(3)-10(4) gDNA copies/reaction. Overall, the platform accurately detected resistance to ciprofloxacin (sensitivity and specificity, 100%), ceftriaxone (sensitivity 100%, specificity 90%), cefixime (sensitivity 92%, specificity 94%), azithromycin and spectinomycin (both sensitivity and specificity, 100%). In conclusion, our methodology accurately detects mutations generating resistance to antibiotics used to treat gonorrhea. Low assay sensitivity prevents direct diagnostic testing of clinical specimens but this method can be used to screen collections of gonococcal isolates for AMR more quickly than with current culture-based AMR testing.

Detection of low energy antimatter with emulsions

Emulsion detectors feature a very high position resolution and consequently represent an ideal device when particle detection is required at the micrometric scale. This is the case of quantum interferometry studies with antimatter, where micrometric fringes have to be measured. In this framework, we designed and realized a new emulsion based detector characterized by a gel enriched in terms of silver bromide crystal contents poured on a glass plate. We tested the sensitivity of such a detector to low energy positrons in the range 10–20 keV . The obtained results prove that nuclear emulsions are highly efficient at detecting positrons at these energies. This achievement paves the way to perform matter-wave interferometry with positrons using this technology.