Formation of polypyrrole and polythiophene within Cu2+- and H+-mordenite hosts studied by EPR and UV-VIS spectroscopy

The reactions of pyrrole and thiophene monomers in copper-exchanged mordenite have been investigated using EPR and UV–VIS absorption spectroscopy. The EPR spectra show a decrease in the intensity of the Cu2+ signal and the appearance of a radical signal due to the formation of oxidatively coupled oligomeric and/or polymeric species in the zeolite host. The reaction ceases when ca. 50% of the copper has reacted and differences in the form of the residual Cu2+ signal between the thiophene and pyrrole reactions suggest a greater degree of penetration of the reaction into the zeolite host for pyrrole, in agreement with previous XPS measurements. The EPR signal intensities show that the average length of the polymer chain that is associated with each radical centre is 15–20 and 5–7 monomer units for polypyrrole and polythiophene, respectively. The widths of the EPR signals suggest that these are at least partly due to small oligomers. The UV–VIS absorption spectra of the thiophene system show bands in three main regions: 2.8–3.0 eV (A), 2.3 eV (B) and 1.6–1.9 eV (D, E, F). Bands A and D–F occur in regions which have previously been observed for small oligomers, 4–6 monomer units in length. Band B is assigned to longer chain polythiophene molecules. We therefore conclude that the reaction between thiophene and copper-loaded mordenite produces a mixture of short oligomers together with some long chain polythiophene. The UV–VIS spectra of the pyrrole system show bands in the regions 3.6 eV (A), 2.7–3.0 eV (B, C) and 1.5–1.9 eV (D, F). Assignments of these bands are less certain than for the thiophene case because of the lack of literature data on the spectra of pyrrole oligomers.

Raman and infrared spectroscopic study of kamphaugite-(Y)

We have studied the carbonate mineral kamphaugite-(Y)(CaY(CO3)2(OH)·H2O), a mineral which contains yttrium and specific rare earth elements. Chemical analysis shows the presence of Ca, Y and C. Back scattering SEM appears to indicate a single pure phase. The vibrational spectroscopy of kamphaugite-(Y) was obtained using a combination of Raman and infrared spectroscopy. Two distinct Raman bands observed at 1078 and 1088cm(-1) provide evidence for the non-equivalence of the carbonate anion in the kamphaugite-(Y) structure. Such a concept is supported by the number of bands assigned to the carbonate antisymmetric stretching mode. Multiple bands in the ν4 region offers further support for the non-equivalence of carbonate anions in the structure. Vibrational spectroscopy enables aspects of the structure of the mineral kamphaugite-(Y) to be assessed.

New Perspectives on the Roman Coinage on the Eastern Limes in the Late Republican and Roman Imperial Period

The Ph.D. thesis discusses the monetary development in Roman Syria and Judaea in the Late Republican and the Early Imperial Period, from a numismatic, archaeological and historical point of view. In effect, the work focuses on the 1st century B.C. to the 1st century A.D., that is, the assumed time of introduction of Roman denarii to the region. The work benefits from the silver coin hoards of Khirbet Qumran recently published by the author. Though discovered as early as 1955 at Qumran, where the famous Dead Sea Scrolls had been found prior to that in 1947, most hoards remained unpublished until 2007. A second important source utilized is the so-called Tax Law from Palmyra in Syria. Its significance lies in the fact that Palmyra used to be one of the most important cities on the Silk Road, along which luxury goods were transported into the Roman Empire and Rome itself. During the research conducted, studies of the provincial coinage of Judaea (A.D. 6-66) shed new light on the authority of the Roman governors in economic and monetary matters in eastern Mediterranean regions. Furthermore, a new suggestion as to the length of the mandate period of Pontius Pilate is made. The extent of Emperor Augustus monetary reforms as well as the military history of Judaea are discussed in the light of new analytical studies, which show that the production of Roman base metal coins appears to have been a highly controlled process, contrary to popular opinion. Statistical calculations related to the coin alloy revealed striking similarities with Roman and other local metalwork found in Israel; a fact previously unknown. Results indicate that both Roman and local metalwork consisted of outstandingly systematized practises and may have exploited the same metal sources. Information: Kenneth Lönnqvist (*25.7.1962) has studied at the University of Helsinki since 1981. Furthermore, Lönnqvist has lived in the Mediterranean countries and the Near East, and made research there at various scientific institutions and universities for ca. 7 years. Contact and sales of thesis: kenneth.lonnqvist@helsinki.fi

Characterisation and early detection of an offtype from micropropagated Lady Finger bananas

An offtype has been identified from micropropagated Lady Finger bananas (Musa spp., AAB group, Pome subgroup) that is characterised by its slow growth and poor bunch size. Bunch weights were approximately 25% those of normal Lady Finger plants and all of the fruit produced was unmarketable. This particular offtype is the most commonly encountered from micropropagated Lady Finger plants and, in 2 instances, blocks of 3000 and 1500 plants were entirely comprised of this single offtype. Detection of offtype plants was possible during establishment and growth of plants in the glasshouse by the presence of chlorotic streaks in the leaves. In more severe cases the streaks coalesced into chlorotic patches that developed thin, necrotic areas that eventually produced holes or splits in the leaves. Symptom expression was not ameliorated by the addition of fertiliser and even though symptoms were similar to severe Ca and B deficiency, both normal and offtype plants had similar levels of these elements in the leaves. The offtype plants were also slow growing in the glasshouse and produced significantly (P<0.05) smaller pseudostems and leaves than normal plants. Offtype plants could be readily detected after 4 weeks deflasking using the presence of chlorotic streaks in the leaves as the main selection criterion. Maximum discrimination was possible between weeks 5–7 and at the 6-leaf stage when all of the offtypes could be detected.

Synthesis and electrocatalytic properties of manganese dioxide for non-enzymatic hydrogen peroxide sensing

Manganese dioxide nanoparticles were synthesized by chemical reduction route at different growth temperatures of 40 degrees C, 80 degrees C, 100 degrees C and were characterized using X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Cyclic Voltammetry (CV) and chronoamperometry (CA) analysis. FESEM results show that on increasing growth temperature the morphology changes from clusters into mixture of rods and flakes. XPS analysis reveals the formation of MnO2. Then these particles were immobilized on Pt electrode. A platinum (Pt) electrode modified with low dimensional MnO2 was investigated as a chronoamperometric (CA) sensor for hydrogen peroxide sensing (H2O2). The sample prepared at 100 degrees C shows good electrocatalytic ability for H2O2 sensing when compared with the samples prepared at 40 degrees C and 80 degrees C. At an operating potential of 0.3 V vs. Ag/AgCl catalytic oxidation of the analyte is measured for chronoamperometric (CA) monitoring. The CA signals are linearly proportional to the concentration of H2O2. It is also found that the morphology of the nanostructure plays a vital role in the detection of H2O2. (C) 2014 Elsevier Ltd. All rights reserved.

A Comparative Study of Early Afterdepolarization-Mediated Fibrillation in Two Mathematical Models for Human Ventricular Cells

Early afterdepolarizations (EADs), which are abnormal oscillations of the membrane potential at the plateau phase of an action potential, are implicated in the development of cardiac arrhythmias like Torsade de Pointes. We carry out extensive numerical simulations of the TP06 and ORd mathematical models for human ventricular cells with EADs. We investigate the different regimes in both these models, namely, the parameter regimes where they exhibit (1) a normal action potential (AP) with no EADs, (2) an AP with EADs, and (3) an AP with EADs that does not go back to the resting potential. We also study the dependence of EADs on the rate of at which we pace a cell, with the specific goal of elucidating EADs that are induced by slow or fast rate pacing. In our simulations in two-and three-dimensional domains, in the presence of EADs, we find the following wave types: (A) waves driven by the fast sodium current and the L-type calcium current (Na-Ca-mediated waves); (B) waves driven only by the L-type calcium current (Ca-mediated waves); (C) phase waves, which are pseudo-travelling waves. Furthermore, we compare the wave patterns of the various wave-types (Na-Ca-mediated, Ca-mediated, and phase waves) in both these models. We find that the two models produce qualitatively similar results in terms of exhibiting Na-Ca-mediated wave patterns that are more chaotic than those for the Ca-mediated and phase waves. However, there are quantitative differences in the wave patterns of each wave type. The Na-Ca-mediated waves in the ORd model show short-lived spirals but the TP06 model does not. The TP06 model supports more Ca-mediated spirals than those in the ORd model, and the TP06 model exhibits more phase-wave patterns than does the ORd model.

Na2.44Mn1.79(SO4)(3): a new member of the alluaudite family of insertion compounds for sodium ion batteries

Sodium-ion batteries have been extensively pursued as economic alternatives to lithium-ion batteries. Investigating the polyanion chemistry, alluaudite structured Na2Fe2II(SO4)(3) has been recently discovered as a 3.8 V positive electrode material (Barpanda et al., Nature Commun., 5: 4358, 2014). Registering the highest ever Fe-III/Fe-II redox potential (vs. Na/Na+) and formidable energy density, it has opened up a new polyanion family for sodium batteries. Exploring the alluaudite family, here we report isotypical Na2+2xMn2-xII(SO4)(3) (x = 0.22) as a novel high-voltage cathode material for the first time. Following low-temperature (ca. 350 degrees C) solid-state synthesis, the structure of this new alluaudite compound has been solved adopting a monoclinic framework (s.g. C2/c) showing antiferromagnetic ordering at 3.4 K. Synergising experimental and ab initio DFT investigation, Na2+2xMn2-xII(SO4)(3) has been found to be a potential high-voltage (ca. 4.4 V) cathode material for sodium batteries.

Incremento de la productividad de frijol (Phaseolus vulgaris L.) a nivel de finca mediante la inoculación con Rhizobium leguminosarum bv. phaseoli

El efecto de una mezcla de tres cepas de Rhizobium leguminosarum biovar phaseoll (CIAT-613, CR-477 y KIM-5) relacionado con los factores limitantes del suelo (P, Ca, Cu, y Zn) sobre la simbiosis en tres variedades de Phaseolus vulgaris L. (DOR-364, ESTELI-90B y FIEVOLUCION-84) fue estudiado en un suelo Molisol y un Aluvial en las localidades de San Diego (Nandaime) y San Lorenzo (La Trinidad, Estelí), respectivamente, bajo condiciones de labranza convencional para ambas localidades. En la localidad de San Lorenzo se trabajó con las variedades DOR-364 y EST-908 con la corrección del cobre (factor A) y el zinc (factor 8), mientras que en la localidad de San Diego, el trabajo se realizó con las variedades DOR-364 y REVOLUCION-84 y la corrección del calcio (factor A) y el fósforo (factor 8), Ambos estudios se llevaron a cabo en época de postrera de 1994. En los dos ensayos la inoculación se hizo directamente a la semilla. Los tratamientos a evaluar fueron los siguientes: Alto nitrógeno, bajo nitrógeno como testigos (sin inocular), mezcla de inoculantes con (-A,-B), (+A,-B), (-A,+B), y (+A,+B) para un total de seis tratamientos por cada variedad. El diseño usado fue de bloques completos al azar (B.C.A). Las variables evaluadas fueron: Número y peso seco de nódulos, peso de materia seca de la planta en R6, peso de mil granos y rendimiento de grano en R9. Los datos se procesaron usando análisis de varianza (ANDEVA) y se utilizó la prueba de rangos múltiples de DUNCAN (P ≤ 0,05). Se observó a nivel general en ambos experimentos que la variedad introducida mostró un mayor rendimiento y que el mejor rendimiento de grano se obtuvo con el tratamiento en el que se usó alta dosis de nitrógeno y sin inocular. Por otro lado el rendimiento de frijol fue afectado negativamente por las aplicaciones de zinc en el caso del experimento en San Lorenzo. Para la localidad de San Diego se obtuvo respuesta positiva a las aplicaciones de fósforo junto con la mezcla de inoculantes usados. En los dos experimentos no se encontró respuesta significativa con el uso de la mezcla de inoculantes relacionados con los elementos limitantes del suelo comparado con los testigos.

Determinación de la capacidad de extracción de nutrientes, acumulación de materia seca y fijación biológica de nitrógeno por cuatro variedades de frijol común (Phaseolus vulgaris L.)

El presente trabajo fue realizado en la estación experimental "La Compañía" Carazo, en época de primera (junio - agosto de 1994), en suelos jóvenes de origen volcánico con altos contenidos de Potasio y deficiente en fósforo. El propósito del experimento fue determinar la variación en la cantidad de Nitrógeno fijado, así como la extracción de nutrientes y acumulación de materia seca, por cuatro variedades de frijol común. Las variedades evaluadas fueron: DOR-364, ESTELÍ 90-A, BRUNCA, CRIOLLA y variedad TESTIGO. El diseño utilizado fue bloques completos al azar (B.C.A) con cuatro tratamientos y cuatro repeticiones. Las variables evaluadas fueron: altura de planta, número de plantas cosechadas por ha, número de vainas por planta, rendimiento de grano, número de nódulos, acumulación de materia seca, concentraciones de nutrientes en la planta y cantidades exportadas por ha. Los datos se procesaron usando análisis de varianza (ANDEVA) y se utilizó la prueba de rangos múltiples de DUNCAN (p 0.05). Los resultados obtenidos se pueden sintetizar de la siguiente forma: La variedad DOR-364 alcanzó una mayor altura así como también una mayor concentración de P y Zn en sus tejidos y acumuló más materia seca, sin embargo disminuyó tanto en el rendimiento de grano como en el número de vainas, además fue deficiente en la población. Esta variedad extrajo la mayor cantidad de N, sin embargo la mayor concentración de este elemento en el follaje la presentó la variedad (testigo. La ESTELÍ 90-A, presentó un mayor número de plantas por ha y un alto rendimiento de grano, fue la variedad más eficiente en la nodulación. Las variedades DOR-364 y ESTELI 90-A exportaron más nutrientes que el resto de las variedades evaluadas. Se desarrolló una tendencia por parte de la variedad TESTIGO a presentar una mayor concentración de K, S, Ca, Mg, Fe, Cu y Mn en sus tejidos en comparación con las otras variedades estudiadas. Se realizaron correlaciones entre cada uno de los elementos y variables en estudio, las cuales mostraron resultados positivos en su mayoría a excepción de la relación entre el número de vainas y los elementos Cu y Fe. El rendimiento se relacionó solamente con el número de nódulos en la segunda evaluación.

Evaluación agronómica y fitosanitaria para la determinación de capacidad de extracción de nutrientes, acumulación de materia seca de dos variedades de frijol común (Phaseolus vulgaris L.) en tres sistemas de labranza (convencional, mínima y cero)

El presente trabajo fue realizado en la estación experimental "La Compañía" Carazo, en época de postrera 1995, en suelos jóvenes de origen de cenizas volcánicas, el suelo es franco-limoso con altos contenidos de potasio y deficientes en fósforo. De acuerdo a sus propiedades, este suelo puede ser considerado adecuado para la mayoría de los cultivos; pH neutro y buen drenaje. El propósito del experimento fue determinar la capacidad de extracción de macro elementos, elementos secundarios, acumulación de materia seca y la dinámica de plagas, enfermedades y enemigos naturales en el cultivo de frijol, para dos variedades de frijol común (Phaseolus vulgaris L.). Las variedades evaluadas fueron: Dor 364, Revolución 84. El diseño utilizado fue en bloques completamente al azar (B.C.A.) con seis tratamientos y cuatro repeticiones, cada tratamiento era un tipo de labranza. Los datos se sometieron a un análisis de varianza (ANOEVA) y se utilizó la prueba de rangos múltiples según Tukey y SNK al 95 por ciento de confianza. Para la recopilación de información sobre plagas y enfermedades los datos se arreglaron en un diseño de parcelas divididas ubic��ndose los tipos de labranza en las parcelas grandes y las variedades en las parcelas pequeñas. El análisis de plagas se hizo usando el paquete estadístico (S.A.S.). El análisis estadísticos de datos se realizó a través de ANDEVA y se separaron los tratamientos por medio de la prueba de S.N.K . Los datos obtenidos se pueden sintetizar de la siguiente forma: La variedad Dor 364 alcanzó una mayor altura en el sistema de labranza mínima, las mayores extracciones de macro elementos y elementos secundarios (P, K, Ca, Mg, y S ), se obtuvo en el sistema de labranza cero + mulch + subsoleo y al mismo tiempo acumuló más materia seca. En cuanto a la variedad Revolución 84 la mayor altura se obtuvo en la labranza cero + mulch, las mayores extracciones y acumulación de materia seca se obtuvo en la labranza convencional La labranza con mejores rendimientos fue la convencional, para ambas variedades evaluadas en el ensayo. La planta indicadora (sorgo) mostró mayor extracción de P, K, Ca, Mg, y S en sus tejidos en comparación con las otras variedades estudiadas En los resultados referentes a plagas de suelo se encontró que labranza mínima presentó mayor número de especies de plagas de suelo. En cuanto insecto plagas de follaje, los mas importantes que se presentaron en el ensayo están; Diabrótica spp., Nodonata spp., y Empoasca spp., la mayor presencia fue de Empoasca spp, la cual estuvo en casi todos los muestreos realizados. De los seis sistemas de labranzas evaluados labranza mínima fue la que mejor disminuyó las poblaciones de insectos plagas del follage. La mayor cantidad de benéficos se observó en labranzas mínima mas incorporación, seguida muy de cerca por labranza convencional más subsoleo. En cuanto a la incidencia y severidad de las enfermedades, fue notorio que hubo poca incidencia en las plantas. Sin embargo en las pocas plantas que hubo presencia de agentes patógenos se observó una alta severidad, la cual fue mayor usando, cero labranzas más mulch.

A preliminary investigation into the effects of a sex-reversal androgen, methyltestosterone, on food utilization and growth of Sarotherodon niloticus (L) fry

Three groups of Sarotherodon niloticus fry were fed for 8 weeks on diets either treated with 17- & methyltestosterone (MT), alcohol (CA), or untreated (CO). Growth rate and food utilization in the different groups were compared. Results indicate that the best growth, Feed Conversion Ratio (FCR), Protein Efficiency Ratio (PER) and Mean Growth Rate (MGR) were obtained with the MT diet. There was no significant difference (P 0.05) in growth and food utilization of the CA and CO fry, nor in the mortality rate of the 3 treatments. The androgen, methyltestosterone promotes growth and protein anabolism without producing toxic effects in S. niloticus

动量相关作用和介质效应对中能重离子碰撞动力学的影响

考虑动量相关作用和介质效应，在入射能量E_L/Nucl. = 100，200，400和800 Mev及碰撞参数b = 1.0，3.0和5.0 fm时，对系统~(40)Ca + ~(40)Ca���数值方法求解BUU方程。发现状态方程的动量相关性增加了集体流，即硬化状态方程；而且增强了核物质的阻止本领。能量小于700 Mev时，动量相关作用和介质效应对集体流和状态方程的影响正好相反，二者竞争的总效果使状态方程变软，能量较高时，两者均使状态方程变硬。它们的影响密切依赖于入射能量和碰撞参数

Effects of bridge ions, DNA species, and developing temperature on flat-lying DNA monolayers

Recently, we have successfully constructed flat-lying DNA monolayers on a mica surface (J. Phys. Chem. B 2006, 110, 10792-10798). In this work, the effects of various factors including bridge ions, DNA species, and developing temperature on the configuration of DNA monolayers have been investigated by atomic force microscopy (AFM) in detail. AFM results show that the species of bridge ions and developing temperature play a crucial role during the formation process. For example, the divalent cation Zn2+ resulted in many DNA chains stuck side by side in the monolayers due to the strong interactions between it and DNA's bases or the mica surface. Most DNA chain's conglutinations disappeared when the developing temperature was higher than 40 degrees C. Cd2+ and Ca2+ produced more compact DNA monolayers with some obvious aggregations, especially for the DNA monolayers constructed by using Ca2+ as the bridge ion. Co2+ produced well-ordered, flat-lying DNA monolayers similar to that of Mg2+. Furthermore, it was found that the flat-lying DNA monolayers could still form on a mica surface when plasmid DNA pBR 322 and linear DNA pBR 322/Pst I were used as the DNA source. Whereas, it was hard to form DNA monolayers on a (3-aminopropyl)triethoxysilane-mica surface because the strong interactions between DNA and substrate prevented the lateral movement of DNA molecules.

Carbon nanotubes selective destabilization of duplex and triplex DNA and inducing B-A transition in solution

Single-walled carbon nanotubes (SWNTs) have been considered as the leading candidate for nano-device applications ranging from gene therapy and novel drug delivery to membrane separations. The miniaturization of DNA-nanotube devices for biological applications requires fully understanding DNA-nanotube interaction mechanism. We report here, for the first time, that DNA destabilization and conformational transition induced by SWNTs are sequence-dependent. Contrasting changes for SWNTs binding to poly[dGdC]:poly[dGdC] and poly[dAdT]:poly[dAdT] were observed. For GC homopolymer, DNA melting temperature was decreased 40 degrees C by SWNTs but no change for AT-DNA. SWNTs can induce B-A transition for GC-DNA but AT-DNA resisted the transition. Our circular dichroism, competitive binding assay and triplex destabilization studies provide direct evidence that SWNTs induce DNA B-A transition in solution and they bind to the DNA major groove with GC preference.

REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.