Robust failure detection filters

The robustness of detection filters applied to the detection of actuator failures on a free-free beam is analyzed. This analysis is based on computer simulation tests of the detection filters in the presence of different types of model mismatch, and on frequency response functions of the transfers corresponding to the model mismatch. The robustness of detection filters based on a model of the beam containing a large number of structural modes varied dramatically with the placement of some of the filter poles. The dynamics of these filters were very hard to analyze. The design of detection filters with a number of modes equal to the number of sensors was trivial. They can be configured to detect any number of actuator failure events. The dynamics of these filters were very easy to analyze and their robustness properties were much improved. A change of the output transformation allowed the filter to perform satisfactorily with realistic levels of model mismatch

A metastatic secretory gastric plasmacytoma with aberrant CD3 expression in a dog

A 10-year-old crossbred dog was presented with a 6-week history of hematemesis, melena, anorexia, and lethargy. Clinical evaluation revealed a gastric mass with a regional lymphadenomegaly as well as a monoclonal gammopathy manifesting as hyperglobulinemia. Cytologic and histopathologic analyses were consistent with a round cell neoplasm; neoplastic cells showed nuclear immunoreactivity for MUM1 and diffuse cytoplasmic reactivity for CD3. Polymerase chain reactions performed on fixed and fresh tissue identified a clonal rearrangement with an IgH primer set. An extramedullary plasmacytoma (EMP) was confirmed by cellular morphology and molecular diagnostics. Following an objective response to chemotherapy, the dog was euthanized 8 months after diagnosis, and a postmortem examination confirmed the clinical findings. This is the first reported case of a monoclonal gammopathy secondary to a gastric EMP coupled with aberrant expression of CD3 in an aggressive plasmacytic tumor, and highlights the utility of molecular diagnostics for classifying atypical hemolymphoid neoplasms

The ferroelectric Mott-Hubbard phase of organic (TMTTF)2X conductors

We present experimental evidences for a ferro-electric transition in the family of quasi one- dimensional conductors (TMTTF)2X. We interpret this new transition in the frame of the combined Mott-Hubbard state taking into account the double action of the spontaneous charge disproportionation on the TMTTF molecular stacks and of the X anionic potentials

Disruption of the RNA modifications that target the ribosome translation machinery in human cancer

Genetic and epigenetic changes deregulate RNA and protein expression in cancer cells. In this regard, tumors exhibit an abnormal proteome in comparison to the corresponding normal tissues. Translation control is a crucial step in the regulation of gene expression regulation under normal and pathological conditions that ultimately determines cellular fate. In this context, evidence shows that transfer and ribosomal RNA (tRNA and rRNA) modifications affect the efficacy and fidelity of translation. The number of RNA modifications increases with the complexity of organisms, suggesting an evolutionary diversification of the possibilities for fine-tuning the functions of coding and non-coding RNAs. In this review, we focus on alterations of modifications of transfer and ribosomal RNA that affect translation in human cancer. This variation in the RNA modification status can be the result of altered modifier expression (writers, readers or erasers), but also due to components of the machineries (C/D or H/ACA boxes) or alterations of proteins involved in modifier expression. Broadening our understanding of the mechanisms by which site-specific modifications modulate ribosome activity in the context of tumorigenesis will enable us to enrich our knowledge about how ribosomes can influence cell fate and form the basis of new therapeutic opportunities

The residues of fruit and vegetable pro-cessing: From “waste” to “resource” of natural phytochemical compounds

The project of Sant’Anna School, in line with the Italian legislation on limiting waste and promoting the redistribution of surpluses and unused goods, aimed to study the potential healthy value of residues obtained from the trans-formation of fruit and vegetable products that represent a cost, as they must be handled, stored and disposed according to stringent actual regulations. Two “model” species (potato and apple) were considered to test the possibility of using industrial processing waste for food applications. The extracts, obtained with “green” methods from potato and apple peels, were evaluated as natural antioxidants in the preparation of minimally processed fresh­cut apple. Results suggest the possibility to use these novel byproduct extracts as valuable alter-native treatments to traditional chemical additives employed for minimally processed apples

Charge transfer in graphene quantum dots coupled with tetrathiafulvalenes

Water-soluble fluorescent graphene quantum dots have been successfully prepared through a top-down approach, that is, starting with graphite, and covalently functionalizing it with p-extended tetrathiafulvalene. Charge transfer investigations reveal noticeably slower charge recombination when compared with exTTF nanoconjugates featuring carbon nanodots, for which a larger presence of trap states is observed

Refinement of computational identification of somatic copy number alterations using DNA methylation microarrays illustrated in cancers of unknown primary

High-throughput genomic technologies are increasingly used in personalized cancer medicine. However, computational tools to maximize the use of scarce tissues combining distinct molecular layers are needed. Here we present a refined strategy, based on the R-package 'conumee', to better predict somatic copy number alterations (SCNA) from deoxyribonucleic acid (DNA) methylation arrays. Our approach, termed hereafter as 'conumee-KCN', improves SCNA prediction by incorporating tumor purity and dynamic thresholding. We trained our algorithm using paired DNA methylation and SNP Array 6.0 data from The Cancer Genome Atlas samples and confirmed its performance in cancer cell lines. Most importantly, the application of our approach in cancers of unknown primary identified amplified potentially actionable targets that were experimentally validated by Fluorescence in situ hybridization and immunostaining, reaching 100% specificity and 93.3% sensitivity

Eight coordinated mononuclear dysprosium complexes of heptadentate aminophenol ligands: the influence of the phenol substituents and the ancillary donors on the magnetic relaxation

The mononuclear complexes [Dy(3Br,5Cl-H3L1,1,4)(D)]·solvate (D = H2O, solvate = 0.25MeOH, 1W·0.25MeOH; D = Py without solvate, 1Py), and [Dy(3NO2,5Br-H3L1,1,4)(H2O)] (2W) were isolated. The crystal structures of 1W·0.25MeOH, 1Py and 2W·2CH3C6H5 show that the DyIII ion is octacoordinated, in N4O4 or N5O3 environments, with distorted geometries, between square antiprism, biaugmented trigonal prism and triangular dodecahedral. A similar environment for the metal ion is shown in the chiral crystals of the diamagnetic yttrium analogue [Y(3Br,5Cl-H3L1,1,4)(MeOH)] (3M), which were spontaneously resolved. Magnetic analyses of the three dysprosium complexes, and their diluted analogous 1W@Y, 1Py@Y and 2W@Y, reveal that none of them seem to relax through an Orbach mechanism at Hdc = 0. However, the three complexes show Orbach relaxation under Hdc = 1000 Oe, and 1Py is the in-field SIM with the highest energy barrier among these complexes, with a Ueff value of 358 K. Analysis of ac magnetic data shows that the electron-withdrawing substituents on the phenol rings of the aminophenol ligands, as well as the auxiliary oxygen donors from water ligands, reduce the energy barriers of the complexes, which is attributed to a charge reduction in the coordinating atoms of the aminophenol donor. Ab initio calculations support the experimental results.Authors thank the Spanish Ministerio de Innovación, Ciencia y Universidades (PGC2018 102052-B-C21) and Xunta de Galicia for financial support. J. C. V also thanks Xunta de Galicia for his Ph.D. fellowship. The authors acknowledge computer resources, technical expertise and assistance provided by the CESGA.S

Tb2, Dy2, and Zn2Dy4 Complexes Showing the Unusual Versatility of a Hydrazone Ligand toward Lanthanoid Ions: a Structural and Magnetic Study

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.8b01251.Three dinuclear complexes, [Tb2(H2daps)2(CH3OH)5.5(H2O)0.5](Cl)2 (Tb2Cl), [Dy2(H2daps)2(Cl)(CH3OH)3(H2O)]Cl (Dy2Cl), and [Dy2(H2daps)2(H2O)6](CF3SO3)2 (Dy2CF3SO3), as well as the heterohexanuclear compound [Zn2Dy4(daps)2(Hdaps)(Cl)3(OH)2(CH3OH)(H2O)5] (Zn2Dy4) (H4daps: 2,6-bis(1-salicyloylhydrazonoethyl)pyridine), which crystallize with different lattice molecules, show their hexa- or heptadentate hydrazone ligands acting with hitherto unknown μ2-κ5:κ1, μ3-κ5:κ4:κ1, μ4-κ5:κ4:κ1:κ1, or μ4-κ5:κ2:κ1:κ1 bridging modes. The single X-ray crystal structures of the dinuclear complexes show nine-coordinated N3O6 environments for lanthanoid atoms in Tb2Cl and Dy2CF3SO3, with distorted geometries, between spherical capped square antiprism and muffin-like, while the dysprosium atoms in Dy2Cl are eight-coordinated, with distorted triangular dodecahedron geometries. In the case of Zn2Dy4, both eight-coordinated, O8 and O7Cl, as well as nine-coordinated N3O6 environments coexist in the crystal structure, with biaugmented trigonal prism, triangular dodecahedron, and muffin-like pseudogeometries. The magnetic study of all the complexes shows that none of the pure samples behaves as a single molecular magnet (SMM) and that the quantum tunnel cannot be removed by dilution of any of the dinuclear complexes, but except in diluted [Y1.904Dy0.096(H2daps)2(Cl)(H2O)4]Cl (Dy2Cl@Y), behaves as a weak field induced SMM. The heterohexanuclear Zn2Dy4 complex also lacks slow relaxation of the magnetization.Financial support from Ministerio de Economía y Competitividad (MINECO, CTQ2014-56312-P), Junta de Andalucía (FQM-195 and Project of excellence P11-FQM-7756), and the University of Granada is gratefully acknowledged. J.C.-V. thanks the Xunta de Galicia for his Ph.D. fellowship.S

Dysprosium-based complexes with a flat pentadentate donor: a magnetic and ab initio study

The reactivity of the well-known pentadentate N3O2 Schiff base H2L (2,6-bis(2-hydroxyphenyliminomethyl)pyridine) towards a lanthanoid metal, in this case DyIII, has been investigated for the first time. This reactivity markedly depends on the pH of the medium and, accordingly, two different complexes, [Dy(HL)(NO3)2]·H2O (1·H2O) and [Dy(L)(NO3)(EtOH)(H2O)]·2H2O (2·2H2O), could be isolated from dysprosium(III) nitrate and H2L. In addition, reaction of H2L with dysprosium(III) chloride in methanol yields [Dy(HL′)2][Dy(L)(Cl2)] (3), where H2L′ ((6-(2-hydroxyphenyliminomethyl)-2-methoxyhydroxymethyl)pyridine) is an N2O2 hemiacetal donor derived from the partial hydrolysis of the H2L ligand, and subsequent addition of the methanol solvent to the carbonyl group. This latter reaction has been firstly observed for a lanthanoid metal. Single crystal X-ray diffraction studies of 1·1.15Py·0.3CH3C6H5, 2·2H2O and 3 show that the Schiff base is acting as a nearly flat pentadentate donor in all the cases, this behaviour being independent of the deprotonation degree of the phenolic oxygen atoms, both mono- or bisdeprotonated. Complexes 1·1.15Py·0.3CH3C6H5 and 2·2H2O show DyN3O6 cores, with distorted geometries closer to spherical tricapped trigonal prism or spherical capped square antiprism for 1·1.15Py·0.3CH3C6H5 and 2·2H2O, respectively. In the case of 3, the [Dy(HL′)2]+ cation shows a dysprosium ion in an N4O4 triangular dodecahedron environment, while the [Dy(L)(Cl2)]− anion displays a DyN3O2Cl2 core with distorted pentagonal bipyramidal geometry. Moreover, attempts to dilute 1·H2O with yttrium yielded single crystals of (Et3NH)[Dy0.09Y0.91(L)(NO3)2] (4), where the Schiff base shows a similar pentadentate coordination mode. Dynamic magnetic studies of 1·H2O, 2·2H2O and 3 show that 2·2H2O and 3 present field-induced slow relaxation of the magnetisation, with Ueff barriers of 46.1(9) and 31.0(7) K for 2·2H2O and 3, respectively, while 1·H2O does not exhibit frequency-dependent peaks of the out of phase susceptibility, even in the presence of an external dc magnetic field. By contrast, the dilute sample 4 behaves as a SIM at zero dc field, with an energy barrier of ca. 49 K. Ab initio calculations using CASSCF methods including spin–orbit effects qualitatively support the obtained magnetic results, indicating that axiality is not the only factor that should be taken into account in order to increase effective energy barriers.Authors thank the Spanish Ministerio de Innovación, Ciencia y Universidades (PGC2018-102052-B-C21, PGC2018-093863-B-C21 and MDM-2017-0767) for financial support. J. C. V thanks Xunta de Galicia for his Ph.D. fellowship. E. R. thanks Generalitat de Catalunya for an ICREA Academia award and for the SGR2017-1289 grant, and S. G. C. for a Beatriu de Pinòs grant. The authors acknowledge computer resources, technical expertise and assistance provided by the CSUC.S