RESUMEN
K2SiH6, crystallizing in the cubic K2PtCl6 structure type (Fm3Ì m), features unusual hypervalent SiH62- complexes. Here, the formation of K2SiH6 at high pressures is revisited by in situ synchrotron diffraction experiments, considering KSiH3 as a precursor. At the investigated pressures, 8 and 13 GPa, K2SiH6 adopts the trigonal (NH4)2SiF6 structure type (P3Ì m1) upon formation. The trigonal polymorph is stable up to 725 °C at 13 GPa. At room temperature, the transition into an ambient pressure recoverable cubic form occurs below 6.7 GPa. Theory suggests the existence of an additional, hexagonal, variant in the pressure interval 3-5 GPa. According to density functional theory band structure calculations, K2SiH6 is a semiconductor with a band gap around 2 eV. Nonbonding H-dominated states are situated below and Si-H anti-bonding states are located above the Fermi level. Enthalpically feasible and dynamically stable metallic variants of K2SiH6 may be obtained when substituting Si partially by Al or P, thus inducing p- and n-type metallicity, respectively. Yet, electron-phonon coupling appears weak, and calculated superconducting transition temperatures are <1 K.
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The on-surface reactions of 10-bromo-10'-(2,6-dimethylphenyl)-9,9'-bianthracene on Au(111) have been investigated by scanning tunneling microscopy and spectroscopy, complemented by theoretical calculations. The reactions afford the synthesis of two open-shell nanographenes (1a and 1b) exhibiting different scenarios of all-carbon magnetism. 1a, an all-benzenoid nanographene with triangulene-like termini, contains a high proportion of zigzag edges which endows it with a low frontier gap and edge-localized states. The dominant reaction product, 1b, is a non-benzenoid nanographene consisting of a single pentagonal ring in a benzenoid framework. The presence of this non-benzenoid topological defect, which alters the bond connectivity in the hexagonal lattice, results in a non-Kekulé nanographene with an unpaired spin, which is detected as a Kondo resonance.
RESUMEN
Nanographenes with sublattice imbalance host a net spin according to Lieb's theorem for bipartite lattices. Here, we report the on-surface synthesis of atomically precise nanographenes and their atomic-scale characterization on a gold substrate by using low-temperature noncontact atomic force microscopy and scanning tunneling spectroscopy. Our results clearly confirm individual nanographenes host a single spin of S=1/2 via the Kondo effect. In covalently linked nanographene dimers, two spins are antiferromagnetically coupled with each other as revealed by inelastic spin-flip excitation spectroscopy. The magnetic exchange interaction in dimers can be well engineered by tuning the local spin density distribution near the connection region, consistent with mean-field Hubbard model calculations. Our work clearly reveals the emergence of magnetism in nanographenes and provides an efficient way to further explore the carbon-based magnetism.
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Triangular zigzag nanographenes, such as triangulene and its π-extended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for high-spin networks with long-range magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the on-surface synthesis and a proof-of-principle experimental study of magnetism in covalently bonded triangulene dimers. On-surface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4-phenylene spacer. The chemical structures of the dimers have been characterized by bond-resolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singlet-triplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling.
RESUMEN
In this work, we demonstrate the bottom-up on-surface synthesis of poly( para-dibenzo[ bc, kl]-coronenylene) (PPDBC), a zigzag edge-encased analog of poly( para-phenylene) (PPP), and its lateral fusion into zigzag edge-extended graphene nanoribbons (zeeGNRs). Toward this end, we designed a dihalogenated di( meta-xylyl)anthracene monomer displaying strategic methyl groups at the substituted phenyl ring and investigated its applicability as precursor in the thermally induced surface-assisted polymerization and cyclodehydrogenation. The structure of the resulting zigzag edge-rich (70%) polymer PPDBC was unambiguously confirmed by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Remarkably, by further thermal treatment at 450 °C two and three aligned PPDBC chains can be laterally fused into expanded zeeGNRs, with a ribbon width of nine ( N = 9) up to 17 ( N = 17) carbon atoms. Moreover, the resulting zeeGNRs exhibit a high ratio of zigzag (67%) vs armchair (25%) edge segments and feature electronic band gaps as low as 0.9 eV according to gaps quasiparticle calculations.
RESUMEN
The electronic and magnetic properties of nanographenes strongly depend on their size, shape and topology. While many nanographenes present a closed-shell electronic structure, certain molecular topologies may lead to an open-shell structure. Triangular-shaped nanographenes with zigzag edges, which exist as neutral radicals, are of considerable interest both in fundamental science and for future technologies aimed at harnessing their intrinsic high-spin magnetic ground states for spin-based operations and information storage. Their synthesis, however, is extremely challenging owing to the presence of unpaired electrons, which confers them with enhanced reactivity. We report a combined in-solution and on-surface synthesis of π-extended triangulene, a non-Kekulé nanographene with the structural formula C33H15, consisting of ten benzene rings fused in a triangular fashion. The distinctive topology of the molecule entails the presence of three unpaired electrons that couple to form a spin quartet ground state. The structure of individual molecules adsorbed on an inert gold surface is confirmed through ultrahigh-resolution scanning tunneling microscopy. The electronic properties are studied via scanning tunneling spectroscopy, wherein unambiguous spectroscopic signatures of the spin-split singly occupied molecular orbitals are found. Detailed insight into its properties is obtained through tight-binding, density functional and many-body perturbation theory calculations, with the latter providing evidence that π-extended triangulene retains its open-shell quartet ground state on the surface. Our work provides unprecedented access to open-shell nanographenes with high-spin ground states, potentially useful in carbon-based spintronics.
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Intracellular leukoproliferative Theileria are unique as eukaryotic organisms that transform the immune cells of their ruminant host. Theileria utilize the uncontrolled proliferation for rapid multiplication and distribution into host daughter cells. The parasite distribution into the daughter cells is accompanied by a tight association with the host cell mitotic apparatus. Since the molecular basis for this interaction is largely unknown, we investigated the possible involvement of the immunodominant Theileria annulata surface protein, TaSP, in the attachment of the parasite to host cell microtubule network. Confocal microscopic analyses showed co-localization of the TaSP protein with alpha-tubulin and reciprocal immuno-co-precipitation experiments demonstrated an association of TaSP with alpha-tubulin in vivo. In addition, the partially expressed predicted extracellular domain of TaSP co-localized with the mitotic spindle of dividing cells and was co-immunoprecipitated with alpha-tubulin in transiently transfected Cos-7 cells devoid of other T. annulata expressed proteins. Pull-down studies showed that there is a direct interaction between TaSP and polymerized microtubules. Analysis of the interaction of TaSP and host microtubulin during host cell mitosis indicated that TaSP co-localizes and interacts with the spindle poles, the mitotic spindle apparatus and the mid-body. Moreover, TaSP was demonstrated to be localized to the microtubule organizing center and to physically interact with gamma-tubulin. These data support the notion that the TaSP-microtubule interaction may be playing a potential role in parasite distribution into daughter host cells and give rise to the speculation that TaSP may be involved in regulation of microtubule assembly in the host cell.
Asunto(s)
Proteínas de la Membrana/metabolismo , Microtúbulos/metabolismo , Mapeo de Interacción de Proteínas , Proteínas Protozoarias/metabolismo , Esquizontes/fisiología , Theileria annulata/patogenicidad , Animales , Células COS , Chlorocebus aethiops , Inmunoprecipitación , Microscopía Confocal , Unión Proteica , Huso Acromático/metabolismo , Huso Acromático/parasitología , Tubulina (Proteína)/metabolismoRESUMEN
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
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The chemical versatility of carbon imparts manifold properties to organic compounds, where magnetism remains one of the most desirable but elusive1. Polycyclic aromatic hydrocarbons, also referred to as nanographenes, show a critical dependence of electronic structure on the topologies of the edges and the π-electron network, which makes them model systems with which to engineer unconventional properties including magnetism. In 1972, Erich Clar envisioned a bow-tie-shaped nanographene, C38H18 (refs. 2,3), where topological frustration in the π-electron network renders it impossible to assign a classical Kekulé structure without leaving unpaired electrons, driving the system into a magnetically non-trivial ground state4. Here, we report the experimental realization and in-depth characterization of this emblematic nanographene, known as Clar's goblet. Scanning tunnelling microscopy and spin excitation spectroscopy of individual molecules on a gold surface reveal a robust antiferromagnetic order with an exchange-coupling strength of 23 meV, exceeding the Landauer limit of minimum energy dissipation at room temperature5. Through atomic manipulation, we realize switching of magnetic ground states in molecules with quenched spins. Our results provide direct evidence of carbon magnetism in a hitherto unrealized class of nanographenes6, and prove a long-predicted paradigm where topological frustration entails unconventional magnetism, with implications for room-temperature carbon-based spintronics7,8.
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The magnetic properties of carbon materials are at present the focus of intense research effort in physics, chemistry and materials science due to their potential applications in spintronics and quantum computing. Although the presence of spins in open-shell nanographenes has recently been confirmed, the ability to control magnetic coupling sign has remained elusive but highly desirable. Here, we demonstrate an effective approach of engineering magnetic ground states in atomically precise open-shell bipartite/nonbipartite nanographenes using combined scanning probe techniques and mean-field Hubbard model calculations. The magnetic coupling sign between two spins was controlled via breaking bipartite lattice symmetry of nanographenes. In addition, the exchange-interaction strength between two spins has been widely tuned by finely tailoring their spin density overlap, realizing a large exchange-interaction strength of 42 meV. Our demonstrated method provides ample opportunities for designer above-room-temperature magnetic phases and functionalities in graphene nanomaterials.
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Herein, we report on the mechanochemical Scholl reaction of dendritic oligophenylene precursors to produce benchmark nanographenes such as hexa-peri-hexabenzocoronene (HBC), triangular shaped C60 and expanded C222 under solvent-free conditions. The solvent-free approach overcomes the bottleneck of solubility limitation in this well-known and powerful reaction. The mechanochemical approach allows tracking the reaction process by in situ pressure measurements. The quality of produced nanographenes has been confirmed by MALDI-TOF mass spectrometry and UV-Vis absorption spectroscopy. This approach paves the way towards gram scale and environmentally benign synthesis of extended nanographenes and possibly graphene nanoribbons suitable for application in carbon based electronics or energy applications.
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Theileria annulata is a tick-transmitted protozoan that causes tropical theileriosis, an often fatal leukoproliferative disorder of cattle. To characterize and identify parasite proteins suitable as diagnostic antigens and/or vaccine candidates, a cDNA clone encoding a macroschizont stage protein was isolated and characterized (here designated TaSP). The gene, present as a single copy within the parasite genome, is transcribed in the sporozoite and schizont stage and codes for a protein of about 315 amino acids, having a predicted molecular weight of 36 kDa. Allelic variants were found within single parasite isolates and between isolates originating from different geographical regions. The N-terminal part contains a predicted signal peptide and the C-terminal section encodes membrane-spanning regions. Comparison of a number of cDNA clones showed that both these sequence regions are conserved while the central region shows both size and amino acid sequence polymorphism. High identity of the N- and C-terminal regions with the polymorphic immunodominant molecule (PIM) of Theileria parva (identity of 93%), the existence of a central polymorphic region and two short introns within genomic clones suggest that the presented gene/protein may be the T. annulata homologue of PIM. However, the central region of TaSP has no significant identity with PIM, contains no repetitive peptide motifs and is shorter, resulting in a lower molecular weight. The existence of the predicted secretion signal peptide and membrane spanning regions suggest that TaSP is located at the parasite membrane.
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Antígenos de Superficie/inmunología , Polimorfismo Genético/genética , Proteínas Protozoarias/inmunología , Theileria annulata/inmunología , Theileria parva/inmunología , Theileriosis/diagnóstico , Theileriosis/inmunología , Vacunas de Subunidad/inmunología , Secuencia de Aminoácidos , Animales , Antígenos de Protozoos/química , Antígenos de Protozoos/genética , Antígenos de Protozoos/inmunología , Antígenos de Superficie/química , Antígenos de Superficie/genética , Western Blotting , Genes Protozoarios/genética , Datos de Secuencia Molecular , Proteínas Protozoarias/química , Proteínas Protozoarias/genética , Vacunas Antiprotozoos/química , Vacunas Antiprotozoos/inmunología , ARN Mensajero/genética , ARN Mensajero/metabolismo , Reacción en Cadena de la Polimerasa de Transcriptasa Inversa , Homología de Secuencia de Aminoácido , Theileria annulata/genética , Theileria annulata/crecimiento & desarrollo , Theileria parva/genética , Theileria parva/crecimiento & desarrollo , Theileriosis/parasitología , Vacunas de Subunidad/químicaRESUMEN
The antigenic proteins of the piroplasm stage of Theileria species (China), the causative agent of theilerosis of small ruminants in China, were analyzed by Western blot, revealing several specific immunoreactive proteins of different predicted molecular weights. Furthermore, sera from Theileria species (China)-infected animals were probed for reactivity with the TaSP protein of T. annulata, for which a homologue has been described in Theileria species (China). Affinity chromatography demonstrated the presence of TaSP-reactive antibodies, and the majority of the sera showed reactivity with this protein both in Western blots and in ELISA. The identified parasite antigens and TaSP will be assessed for their suitability for developing diagnostic methods as well as evaluated for their capacity to stimulated host immune competent cells.
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Antígenos de Protozoos/análisis , Theileria/inmunología , Theileria/patogenicidad , Theileriosis/inmunología , Animales , Western Blotting , China , Cromatografía de Afinidad , Reacciones Cruzadas , Ensayo de Inmunoadsorción Enzimática , Peso Molecular , Proteínas Protozoarias/análisis , Proteínas Protozoarias/inmunología , Rumiantes , Theileriosis/patologíaRESUMEN
In this study potential molecular markers for identification of attenuation in a Theileria lestoquardi-infected cell line to be used in vaccination trials were identified. Two markers associated with attenuation in Theileria annulata vaccine strains were analyzed (metalloproteinase activity and TNF? mRNA expression). The result showed a decreased activity of MMP 9 and decreased mRNA expression of TNF? with increasing passage number. Suppression subtractive hybridization was used to identify potential new markers of attenuation. Random screening revealed nine differentially expressed genes, one from the parasite and eight from the host. Quantitative real time-PCR confirmed mRNA expression of the parasite vacuolar H+ATPase to be downregulated at higher passages.
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Regulación de la Expresión Génica , Metaloproteinasa 9 de la Matriz/metabolismo , Proteínas Protozoarias/genética , Theileria/crecimiento & desarrollo , Theileria/patogenicidad , Factor de Necrosis Tumoral alfa/metabolismo , ATPasas de Translocación de Protón Vacuolares/metabolismo , Animales , Bovinos , Línea Celular , Interacciones Huésped-Patógeno , Metaloproteinasa 9 de la Matriz/genética , Proteínas Protozoarias/metabolismo , Pase Seriado , Ovinos , Factor de Necrosis Tumoral alfa/genética , ATPasas de Translocación de Protón Vacuolares/genéticaRESUMEN
Sheep and goats in northwest China suffer from theileriosis from infection with Theileria sp. (China), resulting in large economic losses. To investigate the immune response to infection with Theileria sp. (China), parameters of cellular and humoral immunity of experimentally infected sheep against two recombinantly expressed Theileria proteins were investigated. The in vitro proliferative response of blood mononuclear cells to a recombinant T. annulata membrane protein and a recombinant Theileria sp. (China) homologue to T. annulata surface protein, both putative membrane proteins, was significantly elevated and significant amounts of specific immunoglobulins were produced against both.
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Proteínas Protozoarias/inmunología , Ovinos/inmunología , Theileriosis/inmunología , Animales , Anticuerpos Antiprotozoarios/biosíntesis , Anticuerpos Antiprotozoarios/sangre , Proteínas Recombinantes/inmunologíaRESUMEN
Intracellular leucoproliferative Theileria are unique as eukaryotic organisms that transform the immune cells of their ruminant host. Theileria utilize the uncontrolled proliferation for rapid multiplication and distribution into host daughter cells. The equal distribution of the schizont into the daughter cells is thought to be accomplished by a tight association with the host cell mitotic apparatus. In this study, we describe a highly conserved novel 37 kD Theileria annulata protein (TaSE). TaSE was found to be localized inside the parasite, the parasite membrane and within the host cell cytoplasm. Moreover, it co-localized at distinct points with host cell microtubules, which was especially apparent during mitosis, where co-localization was found with the centromere, the mitotic spindle and the midbody. Association of TaSE with the host cell tubulin network was corroborated by coimmunoprecipitation and transient transfection experiments. This is the first description of a theilerial protein co-localizing and potentially interacting with a host cell protein. The distribution of TaSE during mitosis makes it a protein to consider as playing a potential role for parasite distribution into daughter host cells.
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Citoplasma/metabolismo , Interacciones Huésped-Parásitos , Proteínas Protozoarias/metabolismo , Theileria annulata/fisiología , Secuencia de Aminoácidos , Animales , Células CHO , Bovinos , Biología Computacional , Cricetinae , Cricetulus , Mitosis , Datos de Secuencia Molecular , Proteínas Protozoarias/química , Proteínas Protozoarias/genética , Análisis de Secuencia de ADN , Theileria annulata/genética , Theileria annulata/crecimiento & desarrollo , Theileria annulata/metabolismo , Tubulina (Proteína)/metabolismoRESUMEN
Theileria annulata and T. parva are protozoa that infect bovine leukocytes which leads to subsequent transformation and uncontrolled proliferation of these cells. It has been proposed that the CKIIalpha subunit of T. parva induces mitogenic pathways of host leukocytes by being exported into the host cell. The evidence for this is the existence of a predicted N-terminal secretion signal-like peptide. We tested this hypothesis by analyzing gene structure, translation, and protein localization of the T. annulata CKIIalpha (TaCKIIalpha). The determined TaCKIIalpha-ORF potentially codes for a 50 kDa protein with an N-terminal extension including a possible signal sequence not present in CKIIalpha proteins of non-Theileria species. However, antisera raised against TaCKIIalpha recognized a protein of a molecular weight of about 40 kDa and, therefore, inconsistent with this predicted molecular weight. We demonstrate by in vitro transcription/translation that this discrepancy is due to translation from a downstream initiation site omitting the putative N-terminal signal sequence and thus excluding the notion that the protein product is secreted via the classical secretory pathway. In corroboration immunofluorescence investigations suggest that the TaCKIIalpha subunit is confined to the parasite schizonts within the host cell. On the basis of the above findings it seems highly unlikely that export via the classical pathway of the parasite CKIIalpha is the way in which this protein possibly contributes to host cell transformation.
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Transformación Celular Neoplásica , Regulación Enzimológica de la Expresión Génica , Biosíntesis de Proteínas , Proteínas Serina-Treonina Quinasas/biosíntesis , Proteínas Serina-Treonina Quinasas/metabolismo , Theileria annulata/enzimología , Secuencia de Aminoácidos , Animales , Quinasa de la Caseína II , División Celular , Línea Celular , Interacciones Huésped-Parásitos , Intrones/genética , Datos de Secuencia Molecular , Peso Molecular , Sistemas de Lectura Abierta/genética , Proteínas Serina-Treonina Quinasas/química , Señales de Clasificación de Proteína , Transporte de Proteínas , Alineación de Secuencia , Especificidad de la Especie , Theileria annulata/genética , Theileria annulata/crecimiento & desarrollo , Theileria annulata/metabolismo , Transcripción GenéticaRESUMEN
A Theileria annulata protein (TaD) exhibiting an N-terminal signal sequence for endoplasmic reticulum membrane translocation and a conserved cysteine-rich region was isolated by screening the mRNA of a T. annulata-infected bovine lymphoblastoid cell line with degenerated primers directed against T. annulata-targeting sequences. The TaD-coding sequence was found to be most closely related to the genomic DNA sequence of T. parva (TIGR database, 72%) and the amino acid sequence of Plasmodium falciparum (41%), P. yoelii yoelii (38%) and Cryptosporidium parvum (36%). The TaD mRNA is expressed within the sporozoite, schizont and merozoite stages of the parasite, implying that it is constitutively transcribed throughout the parasite's life cycle. Allelic variants were found between isolates originating from different geographical regions, however not affecting conserved cysteines. The open reading frame encoded a protein of 19.5 kDa and non-reducing SDS-PAGE analysis demonstrated a homodimeric protein. Using confocal microscopy, the protein was found to be both located in the parasite cytoplasm and to colocalize with a transmembrane protein of the schizonts within infected cells.
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Regulación de la Expresión Génica , Señales de Clasificación de Proteína/genética , Proteínas Protozoarias/genética , Fracciones Subcelulares/metabolismo , Theileria annulata/metabolismo , Secuencia de Aminoácidos , Animales , Bovinos , Línea Celular , Secuencia de Consenso , Datos de Secuencia Molecular , Polimorfismo de Longitud del Fragmento de Restricción , Proteínas Protozoarias/química , Proteínas Protozoarias/metabolismo , Theileria annulata/genética , Theileria annulata/crecimiento & desarrolloRESUMEN
The phylogenetic relationship of Theileria and Babesia species infecting sheep and goats on the basis of their 18S RNA gene structure was addressed in the present study. For this purpose, the complete sequences of the small ribosomal RNA genes of a panel of sheep and goat piroplasm isolates, including T. lestoquardi, T. ovis, T. separata, B. ovis, B. motasi, B. crassa and several novel species, were sequenced and compared. The classification based on the established phylogenetic tree corresponded with traditional systematics and revealed that sheep/goat piroplasm species are of polyphyletic origin. The independent evolution of almost all sheep/goat piroplasms suggests that speciation may have occurred after transfer of the piroplasm-transmitting tick from a primal wild ruminant host to domestic sheep and goats. In accordance with recent reports, our study confirms the existence of at least two additional sheep/goat piroplasm species, designated Theileria sp. 1 (China) and Theileria sp. 2 (China). The recently reported pathogenic sheep/goat Theileria sp. 1 (China) seems to be identical with a Theileria sp. isolated from Japanese serow. Furthermore, our results suggest that T. ovis represents a single species.