Organometallic derivatives of diphosphazanes. 2. Seven-coordinated Group 6 metal tricarbonyl complexes of diphosphazane ligands. X-ray crystal structure of [WI2(CO)3{P(OPh)2}2NPh]

The reactions of the complexes [MI2(CO)3-(NCMe)2] (M = Mo, W) with the diphosphazane ligands RN{P(OPh)2}2 (R = Me, Ph) in CH2Cl2 at room temperature afford new seven-coordinated complexes of the type [MI2(CO)3{P(OPh)2}2NR]. The molybdenum complexes are sensitive to air oxidation even in the solid state, whereas the tungsten complexes are more stable in the solid state and in solution. The structure of the tungsten complex [WI2(CO)3{P(OPh)2}2NPh] has been determined by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system with the space group Pna 2(1), a = 19.372 (2) angstrom, b = 11.511 (1) angstrom, c = 15.581 (1) angstrom, and Z = 4. Full-matrix least-squares refinement with 3548 reflections (I > 2.5-sigma-(I)) led to final R and R(w) values of 0.036 and 0.034, respectively. The complex adopts a slightly distorted pentagonal-bypyramidal geometry rarely observed for such a type of complexes; two phosphorus atoms of the diphosphazane ligand, two iodine atoms, and a carbonyl group occupy the equatorial plane, and the other two carbonyl groups, the apical positions.

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7star, open: Dependence of Tc on hole concentration

Structure and superconducting properties of Tl1?yPbyY1?xCaxSr2Cu2O7 (y=0.0, 0.1, 0.25 and 0.5) , derived from the parent insulator TlYSr2Cu2O7, have been investigated for different values of x. XANES studies show Pb to be in the 4+ state while Tl is in the 3+ state, suggesting thereby that in this series, (x?y) approximately corresponds to the hole concentration. The in-plane Cu---O distance decreases with increase in x for all values of y. The apical Cu---O distance as well as the Tl(Pb)---O(2) distance show anomalies at x=0.5 in the series with y=0.25; at this composition, Tc also reaches a maximum. In general, the composition (value of x) at which the Tc of Tl1?yPbyY1?xCaxSr2Cu2O7 reaches a maximum depends on the Pb content and the maximum Tc itself increases with increase in y, reaching a value of 105 K at y=0.5. More interestingly, a maximum Tc occurs at an (x?y) value of not, vert, similar0.25, which is close to the hole concentration at maximum Tc in other cuprate superconductors containing two CuO2 layers.

Temperature-Sensitive Src-Transformed Mdck Cells nn 3d Cultures as a Model of Malignant Transformation of Epithelial Cells

The equilibrium between cell proliferation, differentiation, and apoptosis is crucial for maintaining homeostasis in epithelial tissues. In order for the epithelium to function properly, individual cells must gain normal structural and functional polarity. The junctional proteins have an important role both in binding the cells together and in taking part in cell signaling. Cadherins form adherens junctions. Cadherins initiate the polarization process by first recognizing and binding the neighboring cells together, and then guiding the formation of tight junctions. Tight junctions form a barrier in dividing the plasma membranes to apical and basolateral membrane domains. In glandular tissues, single layered and polarized epithelium is folded into tubes or spheres, in which the basal side of the epithelial layer faces the outer basal membrane, and the apical side the lumen. In carcinogenesis, the differentiated architecture of an epithelial layer is disrupted. Filling of the luminal space is a hallmark of early epithelial tumors in tubular and glandular structures. In order for the transformed tumor cells to populate the lumen, enhanced proliferation as well as inhibition of apoptosis is required. Most advances in cancer biology have been achieved by using two-dimensional (2D) cell culture models, in which the cells are cultured on flat surfaces as monolayers. However, the 2D cultures are limited in their capacity to recapitulate the structural and functional features of tubular structures and to represent cell growth and differentiation in vivo. The development of three-dimensional (3D) cell culture methods enables the cells to grow and to be studied in a more natural environment. Despite the wide use of 2D cell culture models and the development of novel 3D culture methods, it is not clear how the change of the dimensionality of culture conditions alters the polarization and transformation process and the molecular mechanisms behind them. Src is a well-known oncogene. It is found in focal and adherens junctions of cultured cells. Active src disrupts cell-cell junctions and interferes with cell-matrix binding. It promotes cell motility and survival. Src transformation in 2D disrupts adherens junctions and the fibroblastic phenotype of the cells. In 3D, the adherens junctions are weakened, and in glandular structures, the lumen is filled with nonpolarized vital cells. Madin-Darby canine kidney (MDCK) cells are an epithelial cell type commonly used as a model for cell polarization. Its-src-transformed variants are useful model systems for analyzing the changes in cell morphology, and they play a role in src-induced malignant transformation. This study investigates src-transformed cells in 3D cell cultures as a model for malignant transformation. The following questions were posed. Firstly: What is the role of the composition and stiffness of the extracellular matrix (ECM) on the polarization and transformation of ts v-src MDCK cells in 3D cell cultures? Secondly: How do the culture conditions affect gene expression? What is the effect of v-src transformation in 2D and in 3D cell models? How does the shift from 2D to 3D affect cell polarity and gene expression? Thirdly: What is the role of survivin and its regulator phosphatase and tensin homolog protein (PTEN) in cell polarization and transformation, and in determining cell fate? How does their expression correlate with impaired mitochondrial function in transformed cells? In order to answer the above questions, novel methods of culturing and monitoring cells had to be created: novel 3D methods of culturing epithelial cells were engineered, enabling real time monitoring of a polarization and transformation process, and functional testing of 3D cell cultures. Novel 3D cell culture models and imaging techniques were created for the study. Attention was focused especially on confocal microscopy and live-cell imaging. Src-transformation disturbed the polarization of the epithelium by disrupting cell adhesion, and sensitized the cells to their environment. With active src, the morphology of the cell cluster depended on the composition and stiffness of the matrix. Gene expression studies revealed a broader impact of src transformation than mere continuous activity of src-kinase. In 2D cultures, src transformation altered the expression of immunological, actin cytoskeleton and extracellular matrix (ECM). In 3D, the genes regulating cell division, inhibition of apoptosis, cell metabolism, mitochondrial function, actin cytoskeleton and mechano-sensing proteins were altered. Surprisingly, changing the culture conditions from 2D to 3D affected also gene expression considerably. The microarray hit survivin, an inhibitor of apoptosis, played a crucial role in the survival and proliferation of src-transformed cells.

Structure–property relationship in superconducting cuprates

An examination of the structure and superconducting properties of the various families of cuprates suggests several interesting structural commonalities. Relations between some of the structural parameters of the cuprates and the superconducting transition temperature, T-c, provide useful insights. Variations of T-c on the hole concentration, the in-plane Cu-O and the apical Cu-O distances, as well as the Madelung potentials and bond valence sums are particularly noteworthy. The Cu-O charge-transfer energy appears to be fundamental in determining the properties of cuprates.

The diatom genus Gomphonema Ehrenberg in India: Checklist and description of three new species

We have compiled a checklist of Gomphonema Ehrenberg taxa reported previously from India. From forty-nine references, over 100 Gomphonema taxa have been reported, including 39 new taxon descriptions. In addition to these previous reports of Gomphonema taxa, we describe three new species. G. gandhii Karthick & Kociolek, sp. nov., G. difformum Karthick & Kociolek, sp. nov. and G. diminutum Karthick & Kociolek, sp. nov., all from hill streams of Western Ghats, India. Frustule morphology, as studied in light and scanning electron microscopy, is compared with that of other recently described Gomphonema species from Africa and Asia. All three Indian species have distinctly dilated proximal raphe ends, in addition to differentiated apical pore fields, septa, pseudosepta and a round external stigma! opening. Gomphonema gandhii is linear-lanceolate-clavate, has a wide axial area, and is 19-51 mu m long, 3-7 mu m broad. Gomphonema difformum is smaller than G. gandhii, and has a hyaline area around the headpole. Gomphonema diminuta is much smaller and narrower than the other two species. These species are distinct from their closest congeners by their sizes, shape and structure of the head pole, and striae densities. All these species were described from low nutrient, neutral, low ionic content streams of Western Ghats. As most other species described from tropical region these three species appear to be endemic to India. Moreover, within India they have hitherto only been found in Western Ghats, one of the twelve biodiversity hotspots of the World.

Rotation field in wedge indentation of metals

A study is made of the rotation field in wedge indentation of metals using copper as the model material system. Wedges with apical angles of 60 and 120 are used to indent annealed copper, and the deformation is mapped using image correlation. The indentation of annealed and strain-hardened copper is simulated using finite element analysis. The rotation field, derived from the deformation measurements, provides a clear way of distinguishing between cutting and compressive modes of deformation. Largely unidirectional rotation on one side of the symmetry line with small spatial rotation gradients is characteristic of compression. Bidirectional rotation with neighboring regions of opposing rotations and locally high rotation gradients characterizes cutting. In addition, the rotation demarcates such characteristic regions as the pile-up zone in indentation of a strain-hardened metal. The residual rotation field obtained after unloading is essentially the same as that at full load, indicating that it is a scalar proxy for plastic deformation as a whole.

Spirodiazaselenuranes: synthesis, structure and antioxidant activity

In this paper, the synthesis, characterization and glutathione peroxidase and peroxynitrite scavenging activities of a series of stable spirodiazaselenuranes are described. The spiro compounds were synthesized in good yields by oxidative cyclization of diaryl selenides bearing amide moieties. All the selenides and spiro derivatives were characterized by H-1, C-13 and Se-77 NMR spectroscopy, mass spectral techniques and the structures of some of the spirodiazaselenuranes were confirmed by single crystal X-ray crystallography. The structures reveal that the selenium atom occupies the center of a distorted trigonal bipyramid core with two nitrogen atoms occupying the apical positions and two carbon atoms and the selenium lone pair occupying the equatorial positions. Mechanistic investigations indicate that the spirocyclization occurs via the formation of selenoxide intermediates. The new compounds were evaluated for their glutathione peroxidase (GPx) mimetic activity by using H2O2 as a substrate and glutathione (GSH) as a co-substrate. It was found that the substituents attached to the nitrogen atom of the selenazole ring have a significant effect on the GPx activity. While the introduction of electron withdrawing groups such as -Cl, -Br etc. to the phenyl ring decreases the activity, the introduction of electron donating groups such as -OH, -OMe significantly enhances the GPx activity of both diaryl selenides and spirodiazaselenuranes. In addition to GPx activity, the selenides and spiro derivatives were studied for their ability to inhibit peroxynitrite (PN)-mediated nitration of bovine serum albumin (BSA) and oxidation of dihydrorhodamine 123. These studies indicate that the diarylselenides effectively inhibit the PN-mediated nitration and oxidation reactions by reacting with PN to produce the corresponding spirodiazaselenuranes.

THE KNICKKOPF DOMON DOMAIN IS ESSENTIAL FOR CUTICLE DIFFERENTIATION IN Drosophila melanogaster

The dopamine monoxygenase N-terminal (DOMON) domain is found in extracellular proteins across several eukaryotic and prokaryotic taxa. It has been proposed that this domain binds to heme or sugar moieties. Here, we have analyzed the role of four highly conserved amino acids in the DOMON domain of the Drosophila melanogaster Knickkopf protein that is inserted into the apical plasma membrane and assists extracellular chitin organization. In principal, we generated Knickkopf versions with exchanged residues tryptophan(299,) methionine(333), arginine(401), or histidine(437), and scored for the ability of the respective engineered protein to normalize the knickkopf mutant phenotype. Our results confirm the absolute necessity of tryptophan(299,) methionine(333), and histidine(437) for Knickkopf function and stability, the latter two being predicted to be critical for heme binding. In contrast, arginine(401) is required for full efficiency of Knickkopf activity. Taken together, our genetic data support the prediction of these residues to mediate the function of Knickkopf during cuticle differentiation in insects. Hence, the DOMON domain is apparently an essential factor contributing to the construction of polysaccharide-based extracellular matrices.

Origin of 1/f noise in graphene produced for large-scale applications in electronics

The authors report a detailed investigation of the flicker noise (1/f noise) in graphene films obtained from chemical vapour deposition (CVD) and chemical reduction of graphene oxide. The authors find that in the case of polycrystalline graphene films grown by CVD, the grain boundaries and other structural defects are the dominant source of noise by acting as charged trap centres resulting in huge increase in noise as compared with that of exfoliated graphene. A study of the kinetics of defects in hydrazine-reduced graphene oxide (RGO) films as a function of the extent of reduction showed that for longer hydrazine treatment time strong localised crystal defects are introduced in RGO, whereas the RGO with shorter hydrazine treatment showed the presence of large number of mobile defects leading to higher noise amplitude.

Calcium Permeable AMPA Receptor-Dependent Long Lasting Plasticity of Intrinsic Excitability in Fast Spiking Interneurons of the Dentate Gyrus Decreases Inhibition in the Granule Cell Layer

The local fast-spiking interneurons (FSINs) are considered to be crucial for the generation, maintenance, and modulation of neuronal network oscillations especially in the gamma frequency band. Gamma frequency oscillations have been associated with different aspects of behavior. But the prolonged effects of gamma frequency synaptic activity on the FSINs remain elusive. Using whole cell current clamp patch recordings, we observed a sustained decrease of intrinsic excitability in the FSINs of the dentate gyrus (DG) following repetitive stimulations of the mossy fibers at 30 Hz (gamma bursts). Surprisingly, the granule cells (GCs) did not express intrinsic plastic changes upon similar synaptic excitation of their apical dendritic inputs. Interestingly, pairing the gamma bursts with membrane hyperpolarization accentuated the plasticity in FSINs following the induction protocol, while the plasticity attenuated following gamma bursts paired with membrane depolarization. Paired pulse ratio measurement of the synaptic responses did not show significant changes during the experiments. However, the induction protocols were accompanied with postsynaptic calcium rise in FSINs. Interestingly, the maximum and the minimum increase occurred during gamma bursts with membrane hyperpolarization and depolarization respectively. Including a selective blocker of calcium-permeable AMPA receptors (CP-AMPARs) in the bath; significantly attenuated the calcium rise and blocked the membrane potential dependence of the calcium rise in the FSINs, suggesting their involvement in the observed phenomenon. Chelation of intracellular calcium, blocking HCN channel conductance or blocking CP-AMPARs during the experiment forbade the long lasting expression of the plasticity. Simultaneous dual patch recordings from FSINs and synaptically connected putative GCs confirmed the decreased inhibition in the GCs accompanying the decreased intrinsic excitability in the FSINs. Experimentally constrained network simulations using NEURON predicted increased spiking in the GC owing to decreased input resistance in the FSIN. We hypothesize that the selective plasticity in the FSINs induced by local network activity may serve to increase information throughput into the downstream hippocampal subfields besides providing neuroprotection to the FSINs. (c) 2014 Wiley Periodicals, Inc.

Transient potassium channels augment degeneracy in hippocampal active dendritic spectral tuning

Hippocampal pyramidal neurons express an intraneuronal map of spectral tuning mediated by hyperpolarization-activated cyclic-nucleotide-gated nonspecific-cation channels. Modeling studies have predicted a critical regulatory role for A-type potassium (KA) channels towards augmenting functional robustness of this map. To test this, we performed patch-clamp recordings from soma and dendrites of rat hippocampal pyramidal neurons, and measured spectral tuning before and after blocking KA channels using two structurally distinct pharmacological agents. Consistent with computational predictions, we found that blocking KA channels resulted in a significant reduction in resonance frequency and significant increases in input resistance, impedance amplitude and action-potential firing frequency across the somato-apical trunk. Furthermore, across all measured locations, blocking KA channels enhanced temporal summation of postsynaptic potentials and critically altered the impedance phase profile, resulting in a significant reduction in total inductive phase. Finally, pair-wise correlations between intraneuronal percentage changes (after blocking KA channels) in different measurements were mostly weak, suggesting differential regulation of different physiological properties by KA channels. Our results unveil a pivotal role for fast transient channels in regulating theta-frequency spectral tuning and intrinsic phase response, and suggest that degeneracy with reference to several coexisting functional maps is mediated by cross-channel interactions across the active dendritic arbor.

Caracterización y evaluación preliminar de quince cultivares de maíz (Zea mays L.)

El presente trabajo consistió en la caracterización y evaluación preliminar de 15 cultivares de maíz (Zea mays L.). El germoplasma fue colectado por el programa de Recursos Genéticos Nicaragüenses (REGEN) en diferentes zonas del país, exceptuando al testigo (NB-12) que es una variedad comercial producto de un programa de mejoramiento por parte del MIDINRA y la accesión 2313 que es una introducción de california (U.S.A.). Asimismo el ensayo se realizó en los meses de Junio a Octubre de 1989, en los terrenos del REGEN, ubicados en el Km. 12 ½ carretera norte. El diseño utilizado fue un Bloque Completo al Azar (BCA) con tres repeticiones. Se utilizaron 46 descriptores, tanto cualitativos como cuantitativos; además de incluirse la Distancia Apical como otra variable para caracterizar germoplasma de maíz. Asimismo se determinó un análisis bromatológico de todas las accesiones para evaluar algunos factores nutricionales tales como materia seca, proteína, grasa, fibra bruta y cenizas, obteniéndose resultados de proteína entre el 9% y 12%; grasa entre 3.2 y 4.9% (Tabla 16). Las accesiones caracterizadas demostraron poseer variabilidad genética significativa para la mayor parte de los caracteres considerados. Tal variabilidad puede ser utilizada para programas de selección y mejoramiento o aprovechada directamente para la producción del maíz en Nicaragua.

Comportamiento agronómico de plantas del clon de quequisque Nueva Guinea (Xanthosoma sagittifolium (L) Schott), reproducidas a través de dos técnicas de propagación en condiciones de El Viejo, Chinandega

El objetivo del presente estudio fue evaluar el comportamiento agronómico, a través del análisis de las características morfológicas, fenológicas, de rendimiento y la presencia de enfermedades virales y bacterianas, de plantas del clon de quequisque Nueva Guinea obtenidas de dos técnicas de propagación (CRAS y CONV) y establecidas en condiciones El Viejo, Chinandega. El ensayo se estableció en esquema de diseño de bloques completo al azar, con 4 bloques de 2 tratamientos cada uno. El área de cada bloque fue de 101.61 m2, el de la parcela experimental 50.80 m2, para un área total del experimento de 446.75 m2• La parcela estuvo conformada por 6 surcos, con 12 plantas cada uno (10.08 m de largo). La parcela útil (surcos intermedios 3 y 4) estuvo compuesta de 16 plantas; en las que se evaluaron los surcos intermedios a partir de la planta número 3 hasta la 10. La distancia de siembra fue de 0.84 m x 0.84 m entre surcos y plantas (14,457 plantas/ha). El ANDEVA realizado a las variables morfológicas demostró que las plantas CRAS reportaron los mejores resultados en la mayoría de las evaluaciones. Las plantas convencionales produjeron mayor número de hijos a los 60 y 90 dds, sin embargo a partir de los 120 dds ambos tratamientos fueron estadísticamente similares. Las plantas de ambas técnicas reportaron una tendencia'marcada en disminuir los valores de las variables grosor de pseudotallo a los 180 dds y el número de hojas por planta a los 150 dds. Las plantas CRAS alcanzaron la máxima área foliar a los 150 dds y las plantas CONV a los 180 dds. Las plantas CRAS fueron estadísticamente superiores en el número de cormelos por planta, peso de cormelos por planta (206.07 qq/mz), talla del cormo, a las plantas convencionales (94.20 qq/mz). No se encontraron diferencias estadísticas entre los tratamientos en peso promedio de cormelo, longitud del cormelo, ancho de cormelo y grosor de cormo. Las plantas CRAS presentaron al momento de cosecha cormelos con raíces (65.60 %) y con la yema apical brotada (72.89 %) lo que señala la precocidad de las plantas CRAS, en cambio las plantas convencionales registraron 7 % y 12 % de cormelos con raíces y la yema apical brotada respectivamente. Unido al hecho que los cormelos de estas plantas CRAS presentaron raíces (65.60 %) y yemas apicales brotadas (72.89 %) al momento de la cosecha lo que señala la precocidad de las plantas CRAS en relación con las plantas convencionales las que presentaron en los cormelos 7 % y 12 % de raíces y yemas apicales brotadas respectivamente. Las plantas CONV presentaron 44.44% de plantas con síntomas del DMV y las plantas CRAS 33.38% a los 120 dds; estos valores varian en cada fecha de evaluación Las plantas propagadas convencionalmente registraron 14.93 % de plantas con síntomas de infección con la mancha foliar marginal a los 120 dds, en cambio las plantas CRAS presentaron los máximos valores (11.81 %) a los 180 dds.

Efecto de tres densidades de siembra y cuatro niveles de fertilización nitrogenada sobre el crecimiento, desarrollo y rendimiento del maiz (Zea mays L.) hibrido H-Inta-991, Masatepe, Masaya

El presente estudio se desarrolló en el Centro Experimental Campos Azules (CECA), Masatepe, Masaya; situado a 450 msnm, 12° 19' LN y 86° 04' LO, con el objetivo de contribuir a la producción del maíz evaluando el efecto de tres densidades de siembra (35,000, 50,000 y 62,500 ptas. ha-1) y cuatro niveles de fertilización nitrogenada (0, 75, 150 y 225 kg ha-1de Urea 46% ) sobre el crecimiento, desarrollo y rendimiento del maíz híbrido HN–INTA-991. El ensayo se estableció en junio del año 2003 y se utilizó un diseño en Bloques Completos al Azar (BCA) con arreglos en Parcelas Divididas con cuatro réplicas. A los resultados obtenidos se les realizó un análisis de varianza, y separación de medias a través de la prueba de rangos múltiples de Tukey (8=0.05). También se determinó la respuesta del rendimiento ante la fertilización nitrogenada (Urea 46%) para cada densidad mediante polinomios ortogonales. Los resultados del estudio determinó que el factor densidad mostró efecto significativo sobre la altura y diámetro de la planta; de igual manera tuvo efecto sobre el número de ramas primarias en la panoja y rendimiento de granos, principalmente. De igual manera, la altura a la primera mazorca, área foliar, longitud de panoja, distancia apical y rendimiento de granos, entre otras variables, fueron afectadas por los niveles de fertilización nitrogenada (Urea 46%). Los niveles de nitrógeno (Urea 46%) y la densidad de 50,000 y 62,500 ptas. ha-1 presentaron respuesta lineal y cuadrática, respectivamente. Por otro lado, los resultados del análisis económico determinaron que la mejor relación beneficio-costo se obtiene al hacer uso de la dosis de 75 kg ha-1 con las densidades poblacionales de 50,000 y 62,500 ptas. ha-1.

Caracterización y evaluación de seis híbridos y seis variedades de polinización libre de maíz (Zea mays L.) en El Viejo, Chinandega

Con el propósito de comparar materiales genéticos y contribuir al incremento de la producción de maíz, se desarrolló el presente estudio en la finca “La Frutalosa” en El Viejo, Chinandega. Se estableció un diseño en Bloques Completos al Azar con cuatro bloques y el factor estudio fueron 12 cultivares de maíz (híbridos: HQ-INTA 993, H-53, H-INTA 991, C-343, C-385, HS-56; sintéticos: NB-NUTR INTA, NB-6, NBS, NB-9043; criollos: MAICITO y MAIZON). Los resultados obtenidos fueron objetos de un análisis de varianza (ANDEVA), separación de medias según Tukey (∞=0.05), análisis de correlación y contrastes ortogonales. Los cultivares evaluados presentaron variación en la mayoría de los descriptores de crecimiento y desarrollo. Los materiales criollos obtuvieron mayor altura de planta que los híbridos y sintéticos. En promedio de rendimiento los sintéticos superaron a los criollos e híbridos. Los materiales de mayor rendimiento fueron MAIZON (3534.6 kg ha-1), NB-9043 (2964.8 kg ha-1) y HS-56 (2922.4 kg ha-1). La distancia apical se correlacionó de manera negativa con las variables peso de mazorca, longitud de mazorca y el rendimiento, lo que indica que la mayoría de los materiales evaluados de altos rendimientos tienen poca cobertura de mazorca.