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Two Ru(II) complexes, [Ru(pydppn)(bim)(py)]2+[2; pydppn = 3-(pyrid-2′-yl)-4,5,9,16-tetraaza-dibenzo[a,c]naphthacene; bim = 2,2′-bisimidazole; py = pyridine] and [Ru(pydppn)(Me4bim)(py)]2+[3; Me4bim = 2,2′-bis(4,5-dimethylimidazole)], were synthesized and characterized, and their photophysical properties, DNA binding, and photocleavage were evaluated and compared to [Ru(pydppn)(bpy)(py)]2+(1; bpy = 2,2′-bipyridine). Complexes 2and 3exhibit broad 1MLCT (metal-to-ligand charge transfer) transitions with maxima at ∼470 nm and shoulders at ∼525 and ∼600 nm that extend to ∼800 nm. These bands are red-shifted relative to those of 1, attributed to the π-donating ability of the bim and Me4bim ligands. A strong signal at 550 nm is observed in the transient absorption spectra of 1–3, previously assigned as arising from a pydppn-centered 3ππ* state, with lifetimes of ∼19 μs for 1and 2and ∼270 ns for 3. A number of methods were used to characterize the mode of binding of 1–3to DNA, including absorption titrations, thermal denaturation, relative viscosity changes, and circular dichroism, all of which point to the intercalation of the pydpppn ligand between the nucleobases. The photocleavage of plasmid pUC19 DNA was observed upon the irradiation of 1–3with visible and red light, attributed to the sensitized generation of 1O2by the complexes. These findings indicate that the bim ligand, together with pydppn, serves to shift the absorption of Ru(II) complexes to the photodynamic therapy window, 600–900 nm, and also extend the excited state lifetimes for the efficient production of cytotoxic singlet oxygen.

The oxygen isotopic composition of turtle phosphate from Early (Aptian–Albian) Cretaceous turtles from several North American palaeolatitudes was measured to estimate the isotopic compositions of groundwater δ18Ow. In Earth's history, under greenhouse conditions, researchers have recorded an intensification of the hydrological cycle as global heat was distributed from the equator to the poles via latent heat transport. Previous studies, using pedogenic carbonate nodules, show an increased rainout effect, causing intense depletion in δ18Owat high latitudes due to this phenomenon. This study shows the utility of another palaeo-δ18Owproxy, turtle phosphate oxygen from turtle carapace and plastron. Turtle δ18Opwas sampled from several Early Cretaceous sites. We find that turtle-derived δ18Owvalues range from −3.1 ± 0.9‰ at a palaeolatitude of 29.5° N to −7.2‰ at 40° N. Turtles at the lowest latitude (Arkansas) plot off the carbonate-derived δ18Owgradient; however, turtles at 34° N and 40° N plot within the range of carbonate-derived δ18Ow. Turtles from Arkansas (29.5° N) were likely to have been influenced by marine water and/or enriched Gulf of Mexico water vapour resulting in a deviation from the expected δ18Owgradient. These data are encouraging steps towards using turtles to estimate palaeohydrological dynamics; however, additional analysis of lower- and higher-latitude specimens is necessary to confirm this trend.

A multiproxy approach for evaluating palaeoclimate parameters in deep-time can result in improvements to inter-related factors affecting palaeohydrology. Here we utilize diverse geochemical tools to improve palaeoclimate estimates for the Cedar Mountain Formation (CMF). Prior research utilized stable carbon and oxygen isotopes to develop chemostratigraphic correlations to the late Aptian–early Albian, hypothesized aridity during a positive carbon isotope excursion (CIE) and estimated pCO2through this event. This study refines estimates using petrographical analyses, bulk geochemical proxies for mean annual precipitation (MAP) and clumped isotope palaeothermometry. MAP rates range from 736 to 1042 mm a−1with a slight decrease during the hypothesized aridity event. We interpret warm-biased temperatures (with an average of 32.9°C) that do not vary significantly through the study section. Carbonate nodules are likely to have precipitated in highly evaporative conditions as indicated by the presence of dolomite. Utilizing a simple Rayleigh fractionation model and two estimates of δ18O of water, we suggest that evaporation of 2–57% is necessary to result in an enriched end member δ18Ow. These data suggest that an increase in aridity is a result of lower MAP rates and greater evaporation during seasonal extremes. Lastly, revised pCO2calculations suggest overestimates but indicate a shift towards greater concentrations during the positive CIE.

One of the routes to minimize the environmental impact of plastics waste is the use of bio-sourced and biodegradable alternatives, particularly for packaging applications. Although Polyhydroxyalkanoates (PHA) are attractive candidates for food packaging, they have poor processability, particularly for extrusion film blowing. Thus, one relatively successful alternative has been blending PHA with a biodegradable polymer. This work proposes film blowing of a co-extruded Poly (hydroxybutyrate) (PHB) layer with a poly butylene adipateco- terephtalate (PBAT) layer to enhance bubble stability, mechanical and barrier properties. Co-extrusion is detailed, together with the different strategies followed to improve adhesion between film layers and the PHB content in the films. Films with thicknesses below 50 micron and elongation at break beyond 500% were consistently produced.

In today’s continuously growing demand for components with increasingly smaller dimensions and features, micro-manufacturing is gaining more significance. For the mass production of plastic components with micro-features, injection molding is particularly suitable and still customary in order to keep target costs. Due to high requirements regarding lifetime and resistance to wear, the molds are made of hardened steel. The shaping of these molds involves electrical discharge machining (EDM). This process allows the generation of micro-structures in micrometer range having small inner radii, high dimensional accuracy and extreme aspect ratio independent of the workpiece hardness. As a work tool for EDM, electrodes made of pure copper (Cu) and tungsten reinforced copper (WCu) are commonly used. The shaping of the electrodes is conducted by micro-milling. For an overall understanding of this process chain, the interaction between micro-milling, micro-EDM, and micro-injection molding must be evaluated. This paper provides knowledge on the limits of each process with regard to burr formation, form accuracy, structure size and aspect ratio. Many factors throughout the process chain affect the size of an attainable micro-feature of a final product. The proper selection of the electrode material is a key factor in the process chain. As the feature size of the electrode defines the dimension of the final product shape, the smallest possible structures have to be found during micro-milling. The dimension of the eroded cavity is defined by the feature size of the electrode in combination with the lateral working gap. Eroded cavities with small inner corner radii and steep flanks can be generated when applying flawless and burr-free electrodes. However, using electrodes in inadequate conditions can lead to worse outcomes. The quality and reliability of the final product are determined to a great extent by the design of the injection molding process. Due to the arising vacuum when evacuating the remaining air in the mold, the inflowing melt is being distributed equally. It must be guaranteed that during injection molding, the mold is thermally-controlled. This prevents premature solidification. Through a combination of these two strategies, a form filling rate in micro-cavities up to 100 % is carried out. By deriving an impeccably adapted process chain, a precise micro-molding can be performed. This leads to the capability of manufacturing bars on a final plastic part with a width and height as low as 55 x 100 µm, and a length of 2 mm.

Neuronal/mixed glioneuronal tumors are central nervous system neoplasms composed of neoplastic neuronal cell components or a mixture of glial and neuronal elements. They occur in cerebral hemispheres, posterior fossa, and spinal cord. Compared with other tumors at these locations, diencephalic neuronal/glioneuronal tumors are very rare and therefore not well characterized. We hereby performed clinicopathologic evaluation on 10 neuronal/glioneuronal tumors arising from the diencephalic region. Morphologically, these tumors resemble their histologic counterparts in other locations, except that lymphocytic infiltrates and microcalcifications are more common than Rosenthal fibers or eosinophilic granular bodies. The BRAFV600 mutation rate is 75%. Given the high percentage of samples being small biopsy specimens, the subtle histologic features and molecular findings greatly aided in establishing the pathologic diagnosis in several cases. At a median follow-up of 42 months, 71% of the tumors demonstrated radiological recurrence or progression, with median progression-free survival of 18 months. Recurrence/progression is observed in tumors across different histologic subtypes, necessitating additional therapies in 56% of the cases. Despite their bland histology, diencephalic neuronal/glioneuronal tumors are not clinically indolent. Their frequent recurrences warrant a close follow-up, and the prevalent BRAF mutation makes MAPK pathway inhibition a plausible treatment option when conventional therapies fail.

ABSTRACTThe present work has been conducted in order to assess the mechanical and tribological performance of a ZrN/Mo2N coating deposited onto a H13 steel by means of a closed field unbalanced magnetron-sputtering ion-plating process. The hardness and elastic modulus of the coated system have been determined employing nanoindentation techniques. Dry and wet (3.5 wt-% NaCl solution) sliding wear tests were carried out making use of an alumina ball as counterpart. It has been determined that, during testing under the corrosive solution, the coating experiences a severe abrasive wear mechanism, due to the combined action of the alumina ball, the hard ‘debris’ and a coating localised corrosion attack. On the other hand, it has been shown that the coated system is able to increase the wear resistance of the substrate by more than one order of magnitude, if the wear tests are carried out in air under the same conditions.

Diffuse intrinsic pontine gliomas (DIPGs) are deadly tumors comprising 10%-15% of all childhood CNS cancers. Standard treatment is considered palliative and prognosis is near universal mortality. DIPGs have been classified into genomic subtypes based on histone variants with the lysine to methionine mutation on position 27 of histone tails (K27M). Given the increasing promise of immunotherapy, there have been ongoing efforts to identify tumor-specific antigens to serve as immunologic targets. We evaluated a large cohort of CNS specimens for Wilms' tumor protein (WT1) expression. These specimens include primary pediatric CNS tumors (n = 38 midline gliomas and n = 3 non-midline gliomas; n = 23 DIPG, n = 10 low-grade gliomas, n = 8 high-grade gliomas), and DIPG primary cells. Here, we report the validation of WT1 as a tumor-associated antigen in DIPGs. We further report that WT1 expression is significantly correlated with specific oncohistone variants, with the highest expression detected in the H3.3K27M subgroup. WT1 expression was absent in all control specimens (n = 21). Western blot assays using DIPG primary cells (n = 6) showed a trend of higher WT1 expression in H3.3K27M cells when compared with H3.1 K27M cells and H3 wildtype cells. Our data are the first indication of the association between WT1 and DIPG, with specific upregulation in those harboring oncohistone H3.3K27M.

ABSTRACTSchizophyllumis an important genus of basidiomycetes that, apart from being of genetic and biotechnological interest, is also reported to be a plant and animal pathogen. Schizophyllum communeis the best-known species and the only one reported from clinical specimens thus far, being recovered mainly from the respiratory tract. The aim of this study was to determine the species diversity of 23 clinical isolates of Schizophyllumfrom the United States using multilocus phylogenetic analysis and their in vitrosusceptibilities to six drugs. The markers used for sequencing were the internal transcribed spacer (ITS), a portion of the nuclear large subunit (LSU) of ribosomal DNA, the RNA polymerase II second-largest subunit (RPB2), and the translation elongation factor 1a (EF-1a) gene. The analyses revealed that 22 of the clinical isolates were in the Schizophyllum radiatumclade with high support values and 1 isolate was in the S. communeclade. This is the first report of this species in clinical samples. The two species mentioned above showed very similar morphological features in culture (i.e., white, cottony, unsporulated colonies composed of hyphae with clamp connections), making morphological discrimination between the two impossible. An epitype is designed for S. radiatum, and its sequences have been deposited in GenBank. The antifungal that showed the greatest in vitroactivity against the strains tested was shown to be amphotericin B. In general, the strains of S. radiatumshowed higher MICs than S. commune.

The availability of GODAE Oceanview-type ocean forecast systems provides the opportunity to develop high-resolution, short- to medium-range coupled prediction systems. Several groups have undertaken the first experiments based on relatively unsophisticated approaches. Progress is being driven at the institutional level targeting a range of applications that represent their respective national interests with clear overlaps and opportunities for information exchange and collaboration. The applications include forecasting of the general circulation, hurricanes, extra-tropical storms, high-latitude weather and coastal air–sea interaction. In some cases, research has moved beyond case and sensitivity studies to controlled experiments to obtain statistically significant metrics and operational predictions.

ABSTRACTBalamuthia mandrillarisis a rare cause of human infection, but when infections do occur, they result in high rates of morbidity and mortality. A case of disseminated Balamuthiainfection is presented. Early diagnosis and initiation of recommended therapy are essential for increased chances of successful outcomes.

La aparición de carcinoma urotelial sincrónico en la vía urinaria superior e inferior es infrecuente, y lo es aún más la aparición de forma bilateral. El objetivo de este artículo es describir la técnica quirúrgica de exéresis completa del aparato urinario por vía laparoscópica y añadir diferentes variantes técnicas que permiten mejorar la hemodinámica del paciente durante la cirugía.

En este trabajo se evalúan las vibraciones torsionales de estructuras sobre suelo blando causadas por los efectos combinados de la asimetría estructural y la rotación de la base. Se analiza un sistema suelo-estructura simplificado con 5 grados de libertad. La cimentación se considera enterrada en un estrato uniforme descansando sobre un semiespacio elástico, ante la incidencia inclinada de ondas SH. En lugar de ajustar los máximos momentos torsionantes debidos a los efectos independientes de la asimetría estructural y la rotación de la base, se aplica un nuevo enfoque para el cálculo de la excentricidad de diseño. Específicamente, se obtienen coeficientes de excentricidad torsional compatibles con la máxima respuesta lateral-torsional acoplada, usando un conjunto de temblores de banda angosta característicos de sitios blandos de la Ciudad de México. Se muestra que estos coeficientes no son constantes a lo largo de los ejes principales, sino que dependen de la posición del elemento resistente, por lo que es necesario calcularlos sin asumir una variación lineal como está ocurriendo hasta ahora. Los coeficientes de excentricidad torsional pueden diferir significativamente de los actuales valores reglamentarios, particularmente para estructuras torsionalmente flexibles en las que ambos coeficientes pueden ser negativos. Esto implica que el desplazamiento lateral se reduce por los efectos torsionales.

This multicenter study analyzes the outcome of patients transplanted for hepatocellular carcinoma who were found to have an intrahepatic cholangiocarcinoma at pathology examination, and focuses on the excellent posttransplant outcome of patients with single intrahepatic cholangiocarcinomas ≤2 cm.

This paper reports a multi-layered smart image sensor architecture for feature extraction based on detection of interest points. The architecture is conceived for 3-D integrated circuit technologies consisting of two layers (tiers) plus memory. The top tier includes sensing and processing circuitry aimed to perform Gaussian filtering and generate Gaussian pyramids in fully concurrent way. The circuitry in this tier operates in mixed-signal domain. It embeds in-pixel correlated double sampling, a switched-capacitor network for Gaussian pyramid generation, analog memories and a comparator for in-pixel analog-to-digital conversion. This tier can be further split into two for improved resolution; one containing the sensors and another containing a capacitor per sensor plus the mixed-signal processing circuitry. Regarding the bottom tier, it embeds digital circuitry entitled for the calculation of Harris, Hessian, and difference-of-Gaussian detectors. The overall system can hence be configured by the user to detect interest points by using the algorithm out of these three better suited to practical applications. The paper describes the different kind of algorithms featured and the circuitry employed at top and bottom tiers. The Gaussian pyramid is implemented with a switched-capacitor network in less than 50 μs, outperforming more conventional solutions.

The influence of Mg on the microhardness, microstructure and electrochemical efficiency of Al(Zn/xMg) alloys have been investigated. Al(Zn/xMg) alloys were prepared by metal mould casting method to diminish the process cost and to generate an alloy with homogenous microstructure and less casting porosity. Vickers hardness, X-ray diffraction, scanning electron microscopy and transmission electron microscopy were performed to determine the Mg influence on the AlZn alloy. Electrochemical efficiency was used to relate the influence of Mg with the thermal treatment on the corrosion behavior of the Al(Zn/xMg) alloy. The results reveals the presence of Al32(MgZn)49 phase for two events; the first is when the Mg content is above 5.49% in as-cast condition, and the second after the thermal treatment is carried out at 450 °C for 5 h. The results also show that the microhardness and electrochemical efficiency have been influenced by the presence of Al32(MgZn)49 phase. The addition of Mg modifies the microstructure, increases the content of Al32(MgZn)49 phase and improves the electrochemical efficiency. [Copyright &y& Elsevier]

The effect of peeling methods and storage conditions on unstable physicochemical parameters was studied. Losses of moisture, ascorbic acid, and phenolic compounds with hand peeled were lower than with heat peeled using microwave. A decrease of moisture, ascorbic acid and phenolic compounds was found after 60 days in refrigeration of whole chestnut, and only 3 days in refrigeration of previously homogenized chestnut. The weight and edible portion, moisture, starch, Brix degree, total dietary fiber and non-soluble fiber, protein, ash, pH, acidity, ascorbic acid and total phenolic compounds, were determined in samples from 21 local cultivars in Tenerife island. Chestnut is mainly constituted by starch and sugars, and contributes considerably to the intake of antioxidant compounds such as ascorbic acid and phenolic compounds, as well as fiber and minerals. Significant differences in mean values of the physicochemical parameters were observed among the varieties of chestnuts analyzed. Besides, important differences in the mean values of moisture, starch, Brix degree, different fractions of fiber and phenolic compounds were found according to the zone and municipality of the island.Se estudio el efecto de los metodos de pelado y condiciones de conservacion de las castanas sobre parametros fisicoquimicos inestables. Se observaron perdidas minimas de humedad, acido ascorbico y compuestos fenolicos cuando se realizo el pelado manual en comparacion con el pelado por calor usando microondas. Se constato un descenso de humedad, acido ascorbico y compuestos fenolicos en castanas que fueron conservadas a temperatura de refrigeracion durante 60 dias y despues de tres dias de refrigeracion de muestras de castanas previamente trituradas y homogeneizadas. Se determinaron los siguientes parametros fisicoquimicos: peso y porcion comestible, humedad, almidon, oBrix, fibra alimentaria total e insoluble, proteinas, cenizas, pH, acidez, acido ascorbico y compuestos fenolicos totales en 40 muestras correspondientes a 21 cultivares locales de castanas de la isla de Tenerife. La castana esta constituida principalmente por almidon y azucares aportando una cantidad considerable de compuestos antioxidantes tales como acido ascorbico y compuestos fenolicos, ademas de fibra y minerales. Se observaron diferencias significativas en los valores promedio de los parametros fisicoquimicos analizados entre los cultivares. Asimismo, se encontraron diferencias importantes entre los valores promedio de humedad, almidon, oBrix, diferentes fracciones de fibra y compuestos fenolicos en castanas en funcion del municipio y zona de la isla.Palabras clave: Islas Canarias, Castanea sativa, porcion comestible, pelado, oBrix, fibra, proteina, ceniza, pH, acidez

The concentrations of P, Na, K, Ca, Mg, Fe, Cu, Zn, Mn and Se were determined in 40 samples belonging to local varieties of chestnut produced in Tenerife island. The mineral concentrations arranged according to the following sequence: K > P > Mg > Ca > Fe > Mn > Zn > Cu. The Se was not detected in some samples. The concentrations obtained were lower than most of data found in the literature. Chestnuts significantly contribute to the Cu and Mn intakes, and contribute to the intake of K and Mg. Significant differences in mean concentrations (p < 0.05) between varieties, and between chestnuts from the regions, were observed for all the considered minerals. Significant correlations were observed between P and others studied minerals and also between protein with P, Mg and Zn.Se determino la concentracion de P, Na, K, Ca, Mg, Fe, Cu, Zn, Mn y Se en 40 muestras pertenecientes a 21 cultivares locales de castana producidos en Tenerife. El contenidos de los minerales se ordeno segun la siguiente secuencia: K > P > Mg > Ca > Fe > Mn > Zn > Cu. El Se no se detecto en ninguna muestra. Las concentraciones obtenidas fueron inferiores a la mayoria de los datos encontrados en la bibliografia. La castana contribuye significativamente a la ingesta de Cu y Mn, ademas del aporte de K y Mg. Se detectaron diferencias significativas (p < 0,05), para todos los minerales considerados, entre los valores medios obtenidos en los distintos cultivares y tambien entre municipios de produccion. Se observaron correlaciones significativas entre el P con otros minerales estudiados y entre proteinas con P, Mg y Zn.Palabras clave: Castana, cultivar, Tenerife, minerales, correlaciones

The nuclear factor (NF)-κB system is a promising anticancer target due to its role in oncogenesis and chemoresistance in preclinical models. To provide evidence in a clinical setting on the role of NF-κB in breast cancer, we aimed to study the value of basal NF-κB/p65 in predicting resistance to neoadjuvant chemotherapy, and to characterise the pharmacodynamic changes in NF-κB/p65 expression following chemotherapy in patients with locally advanced breast cancer. Pre- and post-chemotherapy tumour specimens from 51 breast cancer patients treated with anthracycline- and/or taxane-containing neoadjuvant chemotherapy were assayed by immunohistochemistry for NF-κB/p65 subcellular expression. We studied NF-κB/p65, a well-characterised member of the NF-κB family that undergoes nuclear translocation when NF-κB is activated. Activation of NF-κB (i.e. nuclear NF-κB/p65 staining in pre-therapy specimens) was linked to chemoresistance. Patients with NF-κB/p65 nuclear staining in pre-treatment samples had a 20% clinical response rate, while patients with undetected nuclear staining had a 91% response rate to chemotherapy (P= 0.002). Notably, four patients achieved a complete histological response and none of them had pre-treatment NF-κB/p65 nuclear staining. Moreover, the number of patients with NF-κB/p65 activation increased after chemotherapy exposure. It is concluded that NF-κB/p65 activation assayed by immunohistochemistry is a predictive factor of resistance to neoadjuvant chemotherapy in breast cancer patients. Moreover, NF-κB activation was inducible following chemotherapy in a proportion of breast cancer patients. These novel clinical findings strengthen the rationale for the use of NF-κB inhibitors to prevent or overcome chemoresistance in breast cancer.

Femoral revision surgery involves the placement of a stable stem and the regeneration of the damaged bone structure. We retrospectively reviewed 36 cases of femoral revision surgery in which an extensively hydroxyapatite-coated porous stem was implanted with a five-year minimum follow-up. Nine of the cases had type I defects, 12 had type II defects, six had III-A defects and nine had III-B defects. The mean follow-up was 7.7 years (range 5–11). No cases of revision surgery, subsidence or displacement were detected. In 35 cases the integration of the stem had been achieved, the bone structure had been restored and there was no fibrous interface visible between the implant and the bone. The fully hydroxyapatite-coated stems thus proved a valuable alternative for femoral revision surgery in mild and moderate bone defects.

The interpretation of mass spectrometry data for protein identification has become a vital component of proteomics research. However, since most existing software tools rely on protein databases, their success is limited, especially as the pace of annotation efforts fails to keep pace with sequencing. We present a publicly available, web-based version of a software tool that maps peptide mass fingerprint data directly to their genomic origin, allowing for genome-based, annotation-independent protein identification. Keywords: mass spectrometry • genome • peptide mass fingerprint • web interface • gene finding • proteomics

The reaction of the cluster complex [Ru3(μ-Η)(μ3-η²-apyr)(CO)9] (1; Hapyr = 2-aminopyrimidine) with 1,6-diphenoxy-2,4-hexadiyne in refluxing THF gives the trinuclear derivative [Ru3(μ3-η²-apyr)(μ-η³-PhOCH2CH&dbd;CC&tbd1;CCH2OPh)(μ-CO)2(CO)6] (2), which contains an edge-bridging ynenyl ligand. Heating 2 in refluxing toluene leads to an equilibrium mixture of compounds 2 and [Ru3(μ3-η²-apyr)(μ3-η³-PhOCH2CH&dbd;CC&tbd1;CCH2OPh)(CO)8] (3), in which the ynenyl ligand is in a face-capping position. A mechanistic proposal that accounts for the interconversion of 2 and 3 has been obtained from DFT calculations, which have also revealed that isomer 2 is slightly more stable than 3 (3.5 kcal/mol). The bonding of the ynenyl ligands of 2 and 3 to their corresponding triruthenium frameworks has been studied by MO calculations.

In the preparation of high-quality polymeric carbon nanocomposites, the full compatibility of carbon nanotubes as the filler with the matrix polymer is required. For such a purpose, an amino-terminated polyimide, specifically designed to be structurally identical to the matrix polymer, was synthesized and used in the functionalization of carbon nanotubes. The functionalized carbon nanotube samples were analyzed and studied by using a series of techniques, and the results are presented and discussed. These nanotube samples and the matrix polyimide are soluble in the same organic solvents, allowing their intimate mixing in solution and the subsequent fabrication of polyimide-carbon nanotube composite films via wet-casting. According to results from the spectroscopic and electron microscopic characterizations, the carbon nanotubes are homogeneously dispersed in the nanocomposite films.

The reactivity of the triruthenium cluster complex [Ru3(μ3-η³(C,N2)-Habq)(CO)9] (1; H2abqH = 2-amino-7,8-benzoquinoline) with alkynes, tetrafluoroboric acid, dihydrogen, and tertiary silanes and stannanes is reported. The compounds [Ru3(μ3-η³(C,N2)-Habq)(μ3-η²-CCHR)(CO)8] (R = Ph (2), p-tolyl (3), Bu (4), CMe2OH (5), CPh2OH (6), c-C5H8OH (7)), which contain a face-capping vinylidene ligand, have been prepared by treating complex 1 with the corresponding terminal alkynes. However, the reaction of complex 1 with propargyl alcohol leads to [Ru3(μ3-η⁵(C3,N2)-HabqCHCHCH2)(μ-CO)2(CO)6] (8), which bears a new ligand that contains an allylic C3 fragment attached to the C¹⁰ carbon atom of the original Habq ligand. Two compounds have been isolated from the reaction of complex 1 with 1-(trimethylsilyl)penta-1,4-diyne, [Ru3(μ3-η³(C,N2)-Habq)(μ3-η²-CCHCH2CCSiMe3)(CO)8] (9) and Ru3(μ3-η⁵(C3,N2)-HabqCHCHCH2)(μ-CO)2(CO)6] (10). While compound 9 is a vinylidene derivative, analogous to 2−7, compound 10 contains an allylated Habq ligand analogous to 8. The reactions of 1 with internal alkynes lead to mixtures of [Ru3(μ3-η³(C,N2)-Habq)2(μ-CO)(CO)6] (11) and known alkyne-containing ruthenium compounds. Protonation of 1 with tetrafluoroboric acid gives the cationic hydride [Ru3(μ-H)(μ3-η³(C,N2)-Habq)(CO)9][BF4] (12). Free H2abqH and [Ru4(μ-H)4(CO)12] are formed when complex 1 is treated with hydrogen (1 atm, 20 °C). At room temperature, complex 1 does not react with tertiary silanes but reacts with tertiary stannanes to give [Ru3(μ-H)(μ3-η³-Habq-C,N,N)(SnR3)(CO)8] (R = Ph (13), Bu (14)). These compounds slowly release HR at room temperature to render the derivatives [Ru3(μ3-η³(C,N,N)-Habq)(μ-SnR2)(μ-CO)(CO)7] (R = Ph (15), Bu (16)), which contain a bridging stannylene ligand. All this reactivity is quite different from that known for neutral hydrido triruthenium carbonyl clusters containing face-capping N-heterocyclic ligands.

The triruthenium cluster complexes [Ru3(μ-H)(μ3-η²-HapyPh-N,N)(CO)9] (1) and [Ru3(μ-Η)2(μ3-η³-HapyC6H4-N,N,C)2(CO)6] (2) and the hexaruthenium ones [Ru6(μ3-H)2(μ5-η²-apyPh-N,N)(μ-CO)2(CO)14] (3) and [Ru6(μ3-H)(μ5-η³-apyC6H4-N,N,C)(μ-CO)3(CO)13] (4) have been prepared from [Ru3(CO)12] and 2-amino-6-phenylpyridine (H2apyPh). Compound 1 contains a deprotonated HapyPh ligand capping a face of the metal triangle. Compound 2 contains two cyclometalated HapyC6H4 ligands, each spanning a Ru−Ru edge through the N atom of the amido fragment and chelating the remaining Ru atom through both the pyridine N atom and the C atom of the cyclometalated ring. The hexanuclear derivatives 3 and 4 have an uncommon basal edge-bridged square pyramidal metallic skeleton. The bridging ligand of 3 is a doubly deprotonated apyPh ligand which caps the metallic square through the exocyclic N atom, while is attached to the Ru atom that bridges the edge of the square pyramid through the pyridine N atom. Complex 4 is structurally related to 3 but has a cyclometalated phenyl ring. It has been established that compound 2 is formed by reaction of 1 with H2apyPh and that complex 3 is formed by reaction of 1 with [Ru3(CO)12]. While the hydrogenation of 4 gives 3, the thermolysis of 3 gives 4 among other unidentified products. The reaction of the osmium cluster [Os3(CO)10(MeCN)2] with H2apyPh gives a 1:5 mixture of the edge-bridged decacarbonyl derivatives [Os3(μ-Η)(μ-η¹-HapyPh-N)(CO)10] (5) and [Os3(μ-H)(μ-η²-HapyPh-N,N)(CO)10] (6). Both compounds give the face-capped nonacarbonyl derivative [Os3(μ-H)(μ3-η²-HapyPh-N,N)(CO)9] (7) upon irradiation with UV light. Curiously, while complexes 5 and 7 are stable in refluxing toluene, the thermolysis of 6 gives a mixture of 5, 7, and the cyclometalated dihydride [Os3(μ-H)2(μ-η³-HapyC6H4-N,N,C)(CO)9] (8).

Drinking water is currently a scarce world resource, the preparation of which requires complex treatments that include clarification of suspended particles and disinfection. Seed extracts of Moringa oleifera Lam., a tropical tree, have been proposed as an environment-friendly alternative, due to their traditional use for the clarification of drinking water. However, the precise nature of the active components of the extract and whether they may be produced in recombinant form are unknown. Here we show that recombinant or synthetic forms of a cationic seed polypeptide mediate efficient sedimentation of suspended mineral particles and bacteria. Unexpectedly, the polypeptide was also found to possesses a bactericidal activity capable of disinfecting heavily contaminated water. Furthermore, the polypeptide has been shown to efficiently kill several pathogenic bacteria, including antibiotic-resistant isolates of Staphylococcus, Streptococcus, and Legionella species. Thus, this polypeptide displays the unprecedented feature of combining water purification and disinfectant properties. Identification of an active principle derived from the seed extracts points to a range of potential for drinking water treatment or skin and mucosal disinfection in clinical settings. © 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 81: 13–20, 2003.

This paper reports the surface pressure−area isotherms for the new fluorescent probe ω-[6-(N-methyl-N-ethylamino)naphthoyl]undecanoic acid (MANA10-2) obtained by changing experimental variables such as the subphase conditions, pH, temperature, and the compression rate. The surface monolayer technique was used in combination with surface fluorescence measurements. Changes in pH and temperature of the aqueous subphase were found to significantly influence isotherm shape. The fluorescent properties of the molecule were studied both in the monolayer and in the subphase. This allowed us to determine the orientation of MANA10-2 on the surface and revealed that the monolayer is dissolved at both low and high pH values and high temperatures. Monolayers were also examined by Brewster angle microscopy. The morphology and size of the domains formed are clearly governed by temperature and the pH of the aqueous subphases. Only with monolayers spread on pure water at 20 °C was the transition from the liquid phase to the condensed phase observed. This was also the only occasion when the monolayers exhibited high macroscopic uniformity. A large number of small bright nuclei (typical of a densely packed two-dimensional phase or a three-dimensional phase) are formed at low surface pressure in the presence of HCl and NaOH subphases (pH 1 and 9, respectively).

The ruthenium cluster complexes [Ru3(μ3-η³-abq-C,N,N)(CO)9] (1) and [Ru3(μ-H)2(μ3-η³-abq-C,N,N)2(CO)6] (2) (H2abq = 2-amino-7,8-benzoquinoline) have been stepwise prepared from [Ru3(CO)10(MeCN)2]. Both compounds contain cyclometalated abq ligands which span a Ru−Ru edge through the N atom of an amido fragment and chelate the remaining Ru atom through both the quinolinic N atom and the C atom of the cyclometalated ring. For steric reasons, the cyclometalation is responsible for the observation of short Ru−Namido bond lengths. The reaction of the osmium cluster [Os3(CO)10(MeCN)2] with H2abq gives the amido-bridged decacarbonyl derivative [Os3(μ-Η)(μ-η¹-Habq-N)(CO)10] (3). Curiously, while complex 3 is stable in refluxing toluene, the ruthenium analogue of 3 has not been detected. Compounds 1−3 represent the first trinuclear carbonyl clusters containing ligands derived from 2-amino-7,8-benzoquinoline.

Isotherms of surface pressure, π, against mean molecular area, A, were obtained for monolayers of gramicidin A (GA), ethyl palmitate (EP), and mixtures of the two spread at the air−water interface of aqueous solutions of CaCl2 at 15, 20, and 25 °C. Plots of A and of monolayer collapse pressure (πc) against mole fraction of GA (XGA) both suggest miscibility between GA and EP in monolayers at the working temperatures. The morphology of GA, EP, and GA/EP monolayers on aqueous NaCl and CaCl2 solutions at these temperatures was studied by Brewster angle microscopy. The two-dimensional GA/EP solution containing numerous small microdomains of condensed phase was visualized at any surface pressure.

Urinary tract infection (UTI) caused by Corynebacterium urealyticumis a rarely recognised condition in veterinary medicine. This report describes a case in a 13‐month‐old dog which presented with a history of dysuria and haematuria. C urealyticumwas identified as the cause of UTI. The clinical, radiological and ultrasonographic features and the results of urinalysis and urine bacteriological culture are described, as are the therapeutic challenges presented by this particular infection.

The synthesis of the first trinuclear carbonyl clusters containing ligands derived from di(2-pyridyl)amine (Hdpa) has been achieved. Treatment of [Ru3(CO)12] or [Ru3(CO)10(MeCN)2] with di(2-pyridyl)amine (Hdpa) gives the cluster complex [Ru3(μ-Η)(μ-η³-dpa-C,N,N)(CO)9] (1). The dpa ligand in this compound chelates a Ru atom through both pyridinic nitrogens while attached to another Ru atom through the C atom of a metalated pyridine ring, keeping the amino NH fragment uncoordinated. Curiously, the osmium compounds [Os3(μ-Η)(μ-η²-dpa-N,N)(CO)10] (2) and [Os3(μ-Η)(μ3-η²-dpa-N,N)(CO)9] (3), which have been stepwise prepared from [Os3(CO)10(MeCN)2] and Hdpa, contain edge-bridging (2) and face-capping (3) N-deprotonated dpa ligands coordinated through the N atom of a pyridine ring and the N atom of the original amino fragment.

A case of a partial atrial canal defect is described in a nine‐month‐old female English setter. The patient had a large ostium primum atrial septal defect and a concurrent malformation of the mitral valve. Electrocardiographic and radiographic findings were suggestive of marked enlargement of the right heart and pulmonary overcirculation. Definitive diagnosis and assessment of the haemodynamic consequences were made using echocardiography. The magnitude of the left‐to‐right intracardiac shunt was estimated by measuring the pulmonary to systemic flow ratio (Qp/Qs) from Doppler‐derived pulmonary and aortic blood flow. The results of this report suggest that dogs with a partial atrioventricular canal defect and concurrent mild mitral regurgitation may exhibit no clinical signs during the first years of life, even in cases with a Qp/Qs ratio of greater than 2.

The optimization of the conventional synthesis of an important industrial product&sbd;methyl iodide&sbd;by using iron sponge, iodine, and methanol as precursors is presented. The experiments were carried out under different conditions of molar ratio of the reagents, reaction and distillation temperatures, stirring rate, and rate of addition of methanol. It is shown that the highest yield of the product is reached at the molar ratios of methanol/iron of 1.0 and iodine/iron higher of 1.5. The optimal temperature range for this synthesis is located between 53 and 109 °C for which the highest yields were obtained in coincidence with the temperature range at which the formation of FeI2 is also optimal. A relationship between the syntheses of FeI2 and the syntheses of CH3I was elaborated and it was found that the conditions favorable for the syntheses of FeI2 are also necessarily favorable for the syntheses of CH3I.

The μ-1-azavinylidene−μ-alkenyl diruthenium complex [Ru2(μ-η¹:η¹-N&dbd;CPh2)(μ-η¹:η²-PhC&dbd;CHPh)(CO)6] (1) reacts with excess 1-phenyl-1-propyne or 3-hexyne in 1,2-dichloroethane at reflux temperature to give cis-stilbene and the metallacyclic derivatives [Ru2{μ-η³:η⁴-R¹C&dbd;CR²CR¹&dbd;CR²N&dbd;CPh(C6H4)}(μ-CO)(CO)4] (2, R¹ = Ph, R² = Me; 3, R¹ = R² = Et). These compounds contain ligands that result from the ortho metalation of a phenyl group of the original 1-azavinylidene ligand, the release of cis-stilbene, the insertion of the corresponding alkyne molecule into a Ru−N bond, and the insertion of a second alkyne molecule into a Ru−C bond. The reaction of compound 1 with phenylacetylene in 1,2-dichloroethane at reflux temperature gives cis-stilbene, [Ru2{μ-η¹:η²-N&dbd;CPh(C6H4)}(μ-η²:η⁴-PhC&dbd;CHCH&dbd;CPh)(CO)5] (4), and [Ru{η⁵-PhC&dbd;CHCPh&dbd;CHCPh&dbd;CHN&dbd;CPh(C6H4)}(CO)2] (5). The hydrocarbyl ligand of 4, which can be described as a 1,4-diphenylbuta-1,3-diene-1,4-diyl ligand, arises from a head-to-head dimerization of phenylacetylene, whereas the organic ligand of 5 results from an unprecedented insertion of phenylacetylene into a Ru−N bond in addition to a head-to-tail trimerization of phenylacetylene. Thermolysis of compound 1 in refluxing 1,2-dichloroethane gives the tetranuclear derivative [C48H30N2O8Ru4] (6) and the binuclear product [Ru2(μ-η¹:η¹-N&dbd;CPh2)(μ-η³:η⁴-PhCH&dbd;CPhCPh&dbd;CPh)(CO)4] (7). The molecular structure of complex 6 remains unknown. Compound 7 contains a bridging dienyl ligand (with a phenyl substituent η²-coordinated to a Ru atom) that arises from the coupling of diphenylacetylene with the diphenylalkenyl ligand of 1. Mechanistic proposals that account for the formation of complexes 2−7 from compound 1 are given. The new C−N bonds of compounds 2, 3, and 5 are remarkable because they have been formed by migratory insertion of weakly electrophilic alkynes into Ru−N bonds, a process that has hitherto been very seldom observed only with internal alkynes and never with terminal alkynes.