A mechanophysical phase transition provides a dramatic example of colour polymorphism: the tribochromism of a substituted tri(methylene)tetrahydrofuran-2-one

BACKGROUND: Derivatives of fulgides have been shown to have interesting photochromic properties. We have synthesised a number of such derivatives and have found, in some cases, that crystals can be made to change colour on crushing, a phenomenon we have termed "tribochromism". We have studied a number of derivatives by X-ray crystallography, to see if the colour is linked to molecular structure or crystal packing, or both, and our structural results have been supported by calculation of molecular and lattice energies. RESULTS: A number of 5-dicyanomethylene-4-diphenylmethylene-3-disubstitutedmethylene-tetrahydrofuran-2-one compounds have been prepared and structurally characterised. The compounds are obtained as yellow or dark red crystals, or, in one case, both. In two cases where yellow crystals were obtained, we found that crushing the crystals gave a deep red powder. Structure determinations, including those of the one compound which gave both coloured forms, depending on crystallisation conditions, showed that the yellow crystals contained molecules in which the structure comprised a folded conformation at the diphenylmethylene site, whilst the red crystals contained molecules in a twisted conformation at this site. Lattice energy and molecular conformation energies were calculated for all molecules, and showed that the conformational energy of the molecule in structure IIIa (yellow) is marginally higher, and the conformation thus less stable, than that of the molecule in structure IIIb (red). However, the van der Waals energy for crystal structure IIIa, is slightly stronger than that of structure IIIb - which may be viewed as a hint of a metastable packing preference for IIIa, overcome by the contribution of a more stabilising Coulomb energy to the overall more favourable lattice energy of structure IIIb. CONCLUSIONS: Our studies have shown that the crystal colour is correlated with one of two molecular conformations which are different in energy, but that the less stable conformation can be stabilised by its host crystal lattice. Graphical abstractGraphical representation of the structural and colour change in the tribochromic compound (III)

Aerothermal Analysis of Suction Side Film Cooling in a High-Pressure Nozzle Guide Vane Cascade

A specific designed film-cooled nozzle guide vane cascade was tested in a high speed facility to determine the influence of suction side film cooling on the profile loss. Wake traverses with a five-hole probe and measurements of profile pressure distribution were conducted under Ma2th = 0:8 and Re2th ≈ 106 with coolant ejection from two different rows of cooling holes located upstream of the passage throat on the suction surface. In order to clarify the differences in loss behaviour noticed between the investigated film cooling rows, numerical simulations of the experiments were carried out, allowing an in-depth comprehension of the flow phenomena taking place in the mixing layer downstream of the coolant injection point. Additional simulations of the film cooling effectiveness were conducted for both investigated rows

Mid to late Holocene environmental changes along the coast of western Sardinia (Mediterranean Sea)

Multiproxy analysis composed of biostratigraphy and pollen analysis allowed reconstructing the palaeoecological and palaeoenvironmental evolution of the Tirso river coastal plain in Sardinia (NW Mediterranean) in the last 6 millennia. We demonstrated that interplay between littoral and fluvial processes have significantly controlled the environmental evolution of the area and have played a key role in the pattern of historical and prehistorical settlements of this wide portion of western Sardinian coastline. At the end of Neolithic period (ca. 6.0 to 5.5 cal. ka BP) the area close to the shoreline was most likely characterized by large coastal lagoons intermittently connected to the open sea. Such saltwater influence is corroborated by faunal and pollen assemblages found in the landward portion of the Tirso coastal plain up to 2 km inland from the modern shoreline. Our data robustly document the end of the transgressive trend at ca. 5.5 cal. ka BP, and a dominant fluvial sedimentation since Final Neolithic period. At this time, a progradational trend started, causing the seaward migration of shoreline and, consequently, of the barrier-lagoon system. The major landscape modification tracked along the last 6 millennia may also explain the low density of historical and prehistorical remains in the Tirso coastal plain, especially if compared to the nearby rocky area of Sinis Peninsula densely inhabited since the Neolithic. Our data further provide new insights into the Relative Sea Level (RSL) evolution in this sector of the Mediterranean. In particular, we improved the mid-Holocene RSL record in Sardinia, where only scarce data were previously available

Tris-ureas as transmembrane anion transporters

Nine tris-urea receptors (L1–L9) have been synthesised and shown to coordinate to a range of anionic guests both by 1H NMR titration techniques and single crystal X-ray structural analysis. The compounds have been shown to be capable of mediating the exchange of chloride and nitrate and also chloride and bicarbonate across POPC or POPC : cholesterol 7 : 3 vesicle bilayer membranes at low transporter loadings. An interesting dependency of anion transport on the nature of the cation is evidence to suggest that a M+/Cl− cotransport process may also contribute to the release of chloride from the vesicles

Reactivity of the drug methimazole and its iodine adduct with elemental zinc

The reactivity of zinc complexes with N,S-donor molecules may be of relevance to the study of Zn-metalloproteins and -metalloenzymes. In this context, the zinc complex [Zn(MeImSH)2I2] was synthesised by the reaction of zinc powder with the 1 : 1 iodine adduct of the drug methimazole [(MeImSH)·I2]. The molecular structure of the complex, elucidated by X-ray diffraction analysis, showed a tetrahedral zinc(II) centre coordinated by two neutral methimazole units (through the sulfur atoms) and two iodides. From the reaction of MeImSH and Zn powder, the complex [Zn(MeImSH)(MeImS)2] (MeImS = deprotonated form of methimazole) was separated and characterised. An analysis of the crystal packing of the neutral complexes [Zn(MeImSH)2X2] (X = I, Br and Cl) and the ionic complex [Zn(MeImSH)3I]I showed that in all of the complexes the sulfur atom, in addition to binding to the metal centre, contributes to the formation of 1-D chains built via C(4)–HS and N–HX interactions in the neutral complexes, and via C(4)–HS and N–CH3S interactions in the ionic complex [Zn(MeImSH)3I]I. The deprotonation/protonation of the coordinated methimazole units can modulate the coordination environment at the Zn core. From the reaction of complex [Zn(MeImSH)3I]I with a strong non-coordinating organic base, we have shown that, as a consequence of the NH deprotonation of methimazole S-coordinated to zinc(II), the ligand coordination mode changes from S-monodentate to N,S-bridging. Correspondingly, in the complex [Zn(MeImSH)(MeImS)2], the MeImS that displays the N,S-bridging mode at zinc can be N-protonated and thereby changes to the S-monodentate coordination

Food safety considerations in relation to Anisakis pegreffii in anchovies (Engraulis encrasicolus) and sardines (Sardina pilchardus) fished off the Ligurian Coast (Cinque Terre National Park, NW Mediterranean)

Aims: The purpose of this work was to verify whether E. coli is a good indicator of viral contamination in mussels and Adenovirus could represent a better alternative as indicator organism of viral presence to guarantee consumer health protection. Methods and Results: Eighty samples of mussels from La Spezia Gulf were analysed for E. coli, Salmonella, Adenovirus, Norovirus and hepatitis A virus with cultural and biomolecular tests. The results of bacterial parameters showed E. coli within the law’s limits and the absence of Salmonella. Twelve samples were positive for Adenovirus presence, one for Norovirus genogroup II and two for hepatitis A virus. None of these positive mussels was found to be contaminated with more than one virus at the same time. Conclusion: This study showed that there was not a direct correlation between the presence of human pathogenic viruses and bacterial indicators. Significance and Impact of the Study: Both E. coli and Adenovirus cannot be considered valid substitutes for the direct research of human pathogenic viruses in mussels. To improve consumer health protection, the European Commission will provide standardized methods for Norovirus and hepatitis A virus detection as soon as possible

Gravity model in the Korean highway

We investigate the traffic flows of the Korean highway system, which contains both public and private transportation information. We find that the traffic flow T(ij) between city i and j forms a gravity model, the metaphor of physical gravity as described in Newton's law of gravity, P(i)P(j)/r(ij)^2, where P(i) represents the population of city i and r(ij) the distance between cities i and j. It is also shown that the highway network has a heavy tail even though the road network is a rather uniform and homogeneous one. Compared to the highway network, air and public ground transportation establish inhomogeneous systems and have power-law behaviors.Comment: 13 page

Factors associated with false-negative cervical cytopathological results

Purpose: to evaluate whether factors related to the adequacy of the sample, cell pattern and cytomorphological criteria are associated with false-negative (FN) results of cervical cytopathology during routine examinations. Methods: this is a case-control study in which the study group included 100 cytopathologic smears with FN results detected during systematic internal quality control consisting of 100% rapid review. For each FN result detected, two smears with a true-positive diagnosis were identified by the same cytotechnician and these constituted the control group, making a total sample size of 300 smears. The variables were established in accordance with the criteria defined for the analysis of sample adequacy, cell pattern and cytomorphological analyzed criteria. The results were evaluated using bivariate analysis and logistic regression with stepwise variable selection criteria expressed in OR (95%). Results: the number of atypical cells, the appearance of nuclear chromatin, and the distribution and presentation of atypical cells in the smear were the variables that showed the greatest risk for FN results with OR of 9.6, 4.2, 4.4, and 3.6, respectively. Inflammatory processes and the presence of blood in the smear were also identified as variables that influence the risk of FN results. Conclusions: the majority of the factors associated with FN results are dependent on the conditions and techniques of sample collection, since in the majority of cases, the lesion may not be adequately represented in the smear. Confounding factors such as blood and inflammatory processes may also impair analysis. With respect to cytomorphological alterations, thin chromatin strand was the variable that indicated the greatest risk of FN results.Verificar se, no escrutínio de rotina, fatores relacionados com a adequabilidade da amostra, padrão celular e critérios citomorfológicos estão associados a resultados falso-negativos (FN) dos exames citopatológicos. Métodos: trata-se de um estudo caso-controle, no qual o grupo de casos incluiu 100 esfregaços citopatológicos com um resultado FN que foi detectado pela sistemática de controle interno da qualidade com revisão rápida de 100%. Para cada resultado FN detectado foram identifi cados,pelo mesmo citotécnico, dois esfregaços com um diagnóstico verdadeiro-positivo e este grupo foi considerado controle, totalizando uma casuística de 300 esfregaços. As variáveis analisadas foram estabelecidas de acordo com os critérios defi nidos para a análise da adequabilidade da amostra, padrão celular e critérios citomorfológicos. Os resultados foram avaliados por análise bivariada e regressão logística com critério de seleção de variáveis stepwise e expressos em OR (95%). Resultados: o número de células atípicas, aspecto da cromatina nuclear, distribuição e apresentação de células atípicas no esfregaço apresentaram risco maior para resultados FN, com OR de 9,6; 4,2; 4,4 e 3,6, respectivamente. Processo infl amatório e presença de sangue no esfregaço mostraram também risco para os resultados FN. Conclusões: a maioria dos fatores associados à liberação de um resultadoFN é dependente das condições e técnicas de coleta de material, pois, em grande parte, a lesão pode não estar adequadamente representada no esfregaço, e também fatores obscurecedores como sangue e processo infl amatório podem prejudicar a análise. Quanto às alterações citomorfológicas, cromatina fi na foi a característica que apresentou maior risco para resultados FN288479485To evaluate whether factors related to the adequacy of the sample, cell pattern and cytomorphological criteria are associated with false-negative (FN) results of cervical cytopathology during routine examinations. Methods: this is a case-control study in which the study group included 100 cytopathologic smears with FN results detected during systematic internal quality control consisting of 100% rapid review. For each FN result detected, two smears with a true-positive diagnosis were identified by the same cytotechnician and these constituted the control group, making a total sample size of 300 smears. The variables were established in accordance with the criteria defined for the analysis of sample adequacy, cell pattern and cytomorphological analyzed criteria. The results were evaluated using bivariate analysis and logistic regression with stepwise variable selection criteria expressed in OR (95%). Results: the number of atypical cells, the appearance of nuclear chromatin, and the distribution and presentation of atypical cells in the smear were the variables that showed the greatest risk for FN results with OR of 9.6, 4.2, 4.4, and 3.6, respectively. Inflammatory processes and the presence of blood in the smear were also identified as variables that influence the risk of FN results. Conclusions: the majority of the factors associated with FN results are dependent on the conditions and techniques of sample collection, since in the majority of cases, the lesion may not be adequately represented in the smear. Confounding factors such as blood and inflammatory processes may also impair analysis. With respect to cytomorphological alterations, thin chromatin strand was the variable that indicated the greatest risk of FN result

Coordination Chemistry and Sensing Properties Towards Anions and Metal Ions of a Simple Fluorescent Urea

The coordination and sensing properties towards anions and transition metal ions of the simple novel fluorescent urea 1-(2-aminophenyl)-3-(naphthalen-1)-yl)urea (L) were investigated in solution, and in the solid state. An electron donating amine group in the molecular skeleton of L decreased the acidity of the urea NHs that are usually deprotonated by basic anions and allowed for a good degree of affinity towards fluoride in DMSO-d6-0.5 %H2O. Moreover, the amine moiety acted as a further binding group for metal ions. Indeed, L was able to bind Zn2+ both in solution and in the solid state, and to respond to the presence of this metal ion in MeCN with an enhancement of the fluorescence emission. Although solution studies evidenced the formation of a 1 : 1 complex of L with Zn2+, complexes with a 2 : 1 ligand-to-metal stoichiometry were isolated in the solid state. DFT calculations helped to clarify the stability reasons behind these results

Spatial correlations in attribute communities

Community detection is an important tool for exploring and classifying the properties of large complex networks and should be of great help for spatial networks. Indeed, in addition to their location, nodes in spatial networks can have attributes such as the language for individuals, or any other socio-economical feature that we would like to identify in communities. We discuss in this paper a crucial aspect which was not considered in previous studies which is the possible existence of correlations between space and attributes. Introducing a simple toy model in which both space and node attributes are considered, we discuss the effect of space-attribute correlations on the results of various community detection methods proposed for spatial networks in this paper and in previous studies. When space is irrelevant, our model is equivalent to the stochastic block model which has been shown to display a detectability-non detectability transition. In the regime where space dominates the link formation process, most methods can fail to recover the communities, an effect which is particularly marked when space-attributes correlations are strong. In this latter case, community detection methods which remove the spatial component of the network can miss a large part of the community structure and can lead to incorrect results.Comment: 10 pages and 7 figure