Exploring conformational energy landscape of glassy disaccharides by CPMAS 13C NMR and DFT/GIAO simulations. I. Methodological aspects

The aim of this article is to assess the ability of chemical shift surfaces to provide structural information on conformational distributions of disaccharides in glassy solid state. The validity of the general method leading to a simulation of inhomogeneous 13C chemical shift distributions is discussed in detail. In particular, a proper consideration of extrema and saddle points of the chemical shift map correctly accounts for the observed discontinuities in the experimental CPMAS spectra. Provided that these basic requirements are met, DFT/GIAO chemical shift maps calculated on relaxed conformations lead to a very satisfactory description of the experimental lineshapes. On solid-state trehalose as a model of amorphous disaccharide, this simulation approach defines unambiguously the most populated sugar conformation in the glass, and can help in discriminating the validity of different models of intramolecular energy landscape. Application to other molecular systems with broad conformational populations is foreseen to produce a larger dependence of the calculated chemical shift distribution on the conformational map

Rich polymorphism of a rod-like liquid crystal (8CB) confined in two types of unidirectional nanopores

We present a neutron and X-rays scattering study of the phase transitions of 4-n-octyl-4'-cyanobiphenyl (8CB) confined in unidirectional nanopores of porous alumina and porous silicon (PSi) membranes with an average diameter of 30 nm. Spatial confinement reveals a rich polymorphism, with at least four different low temperature phases in addition to the smectic A phase. The structural study as a function of thermal treatments and conditions of spatial confinement allows us to get insights into the formation of these phases and their relative stability. It gives the first description of the complete phase behavior of 8CB confined in PSi and provides a direct comparison with results obtained in bulk conditions and in similar geometric conditions of confinement but with reduced quenched disorder effects using alumina anopore membranesComment: Accepted in EPJ E - Soft Matte

A detailed study of the diastereoselective catalytic hydrogenation of 6-hydroxytetrahydroisoquinoline-(3R)-carboxylic ester intermediates

A key step towards a highly-selective antagonist of ionotropic glutamate receptors entails the diastereoselective arene hydrogenation of an enantiopure tetrahydroisoquinoline. An extensive screen using parallel reactors was conducted and led to the discovery of several Pd/C catalysts giving high yield and improved diastereoselectivity from 75 : 25 to 95 : 5. A detailed kinetic study of the best system was performed and supports the reduction occuring in two-steps.

Tracking the phase-transition energy in disassembly of hot nuclei

In efforts to determine phase transitions in the disintegration of highly excited heavy nuclei, a popular practice is to parametrise the yields of isotopes as a function of temperature in the form $Y(z)=z^{-\tau}f(z^{\sigma}(T-T_0))$, where $Y(z)$'s are the measured yields and $\tau, \sigma$ and $T_0$ are fitted to the yields. Here $T_0$ would be interpreted as the phase transition temperature. For finite systems such as those obtained in nuclear collisions, this parametrisation is only approximate and hence allows for extraction of $T_0$ in more than one way. In this work we look in detail at how values of $T_0$ differ, depending on methods of extraction. It should be mentioned that for finite systems, this approximate parametrisation works not only at the critical point, but also for first order phase transitions (at least in some models). Thus the approximate fit is no guarantee that one is seeing a critical phenomenon. A different but more conventional search for the nuclear phase transition would look for a maximum in the specific heat as a function of temperature $T_2$. In this case $T_2$ is interpreted as the phase transition temperature. Ideally $T_0$ and $T_2$ would coincide. We invesigate this possibility, both in theory and from the ISiS data, performing both canonical ($T$) and microcanonical ($e=E^*/A$) calculations. Although more than one value of $T_0$ can be extracted from the approximate parmetrisation, the work here points to the best value from among the choices. Several interesting results, seen in theoretical calculations, are borne out in experiment.Comment: Revtex, 10 pages including 8 figures and 2 table

Genotyping of Bulgarian Vitis vinifera L. cultivars by microsatellite analysis

A characterization of the Bulgarian grapevine genepool (Vitis vinifera L. cultivars) was initiated through microsatellite analysis. Seventy four wine and table grapevine varieties from the National List of Cultivars, were analyzed at 9 microsatellite loci: VVS2, ssrVvUCH11, ssrVvUCH 29, ssrVrZAG21, ssrVrZAG47, ssrVrZAG62, ssrVrZAG64, ssrVrZAG79 and ssrVrZAG83. The high genetic diversity (78 %) allowed accurate identification and discrimination of the cultivars. The low PI value (1.201 x 10-8) reflects the high discriminative power of the chosen set of markers for the investigated population. Based on the microsatellite allele data, two pairs of old native varieties, Misket Cherven and Misket Vrachanski; Tamyanka and Tamyanka tvarda, were considered distinct cultivars. The synonymy ofTamyanka, Italian Moscato Bianco and Greek Moschato Kerkyras andPamid and Greek Pamidi was verified, while the putative synonymy of Mavrud and Greek Mavroudi Arachovis was rejected.Further utilization of microsatellite profiling in the management of the Bulgarian grapevine genepool is discussed.

An unknown trees die back caused by Pseudomonas species in Switzerland

A model for tree pathogen diagnosis – Prunus domestica L. has been studied against pathogenic bacteria. An orchard of 110 trees of P. domestica showed dying back symptoms in May 2009 and nineteen of these trees were eradicated and burnt for prophylaxis. No symptoms correlated with those caused by pathogens previously observed in stone fruit die back in Europe or elsewhere (Pseudomonas syringae pv syringae van Hall, Pseudomonas syringae pv morsprunorum Lazarowtz, Phytophthora sp., Diaporthe perniciosa Marchal., phytoplasma or viruses) were not found. Interestingly, cutting the trunk in transversal sections allowed the observation of stem heart necrosis which was mostly important at the grafting point. Isolations from necrotic stem heart allowed to identify anot yet described Pseudomonas species not related to P. syringae. The method described in the paper for isolation of pathogenic bacteria and their quick an reliable identification can be also applied for detection of pathogens in forest tree plantations.Przemysław Szmi

Differences in daptomycin and vancomycin ex vivo behaviour can lead to false interpretation of negative blood cultures

AbstractIn clinical studies on bacteraemia, the negativity of blood cultures is an important endpoint for comparing the efficacy of different therapeutic regimens. In FAN° anaerobic blood culture medium (BacT/ALERT system), daptomycin displayed increased MIC against Staphylococcus aureus and improved abolishment of its carryover effect in charcoal when compared with vancomycin. Differences between these two drugs can lead to a false interpretation of negative blood cultures. To compare different antibiotic regimens for the treatment of bacteraemia, preliminary studies are mandatory to ensure that ex vivo antibiotic behaviour is similar in the blood-culture system used

Graphic Classes in the Worldwide Classroom: A Comparison of Two MOOC Experiences

Graphics are present in the day-to-day professional practice of architects and engineers, not only to receive and transmit information, but also to design and create. Students who are accepted on university courses have varied curriculum vitae, and some may initially lack skills. Consequently, engineering schools have developed a Massive Open Online Course (MOOC) entitled “The Language of Engineering” (ELI), which reviews basic geometry concepts and develops spatial intelligence, among others. The Barcelona School of Architecture has produced “From reality to design. From design to augmented reality” (RA), which covers topics including traditional architectural representation and the latest techniques. The goal of this study was to explain and analyse the main characteristics and learning strategies of these two MOOC (strengths, weaknesses and opportunities for improvement). The results show that although strategies vary depending on the subjects, the contents and exercises should be practical and adapted to students (interests, level, time availability and aesthetics), always considering motivation as a key point (gamification). These topics have been found to have a considerable influence on the success of a MOOC. Therefore, the conclusions should be considered in subsequent versions of these courses and other MOOCs.Postprint (author's final draft

Phytophthora polonica, a new species isolated from declining Alnus glutinosa stands in Poland

In a survey of Phytophthora associated with alder decline in Poland, several isolates of a homothallic Phytophthora spet al, which could not be assigned to other taxa including Phytophthora alni subspecies, were consistently recovered from rhizosphere soil samples. Their morphology and pathogenicity, as well as sequence data for three nuclear regions (internal transcribed spacer rDNA, elongation factor-1α and β-tubulin) and a coding mitochondrial DNA region (nadh1), were examined. The new Phytophthora species is characterized by the moderate to slow growth rate of its colony in carrot agar at 20°C, high optimal (c. 30°C) and maximum (c. 38°C) growth temperatures, formation of catenulate, often lateral, hyphal swellings, large chlamydospores in agar media and in soil extract, persistent, ovoid to ellipsoid nonpapillate sporangia and large oogonia with paragynous and sometimes amphigynous antheridia. Phytophthora polonica was slightly pathogenic to alder twigs and not pathogenic to trunks of several tree species. In a phylogenetic analysis using either Bayesian inference or maximum likelihood methods, P. polonica falls in clade 8 ‘sensu Kroon (2004)' of Phytophthor