Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2 `-bipyridine

The synthesis of the heterobinuclear copper-zinc complex CuZn(bz)(3)(bpy)(2)]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 angstrom. The complex is normal paramagnetic having mu(eff) value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants A(av) = 63 x 10(-4) cm(-1), characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g(parallel to) = 2.254 and g(perpendicular to) =2.071 and A(parallel to) = 160 x 10(-4) cm(-1). The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution. (C) 2014 Elsevier B.V. All rights reserved.

Wave propagation of phonon and phason displacement modes in quasicrystals: Determination of wave parameters

The paper presents the study of wave propagation in quasicrystals. Our interest is in the computation of the wavenumber (k(n)) and group speed (c(g)) of the phonon and phason displacement modes of one, two, and three dimensional quasicrystals. These wave parameter expressions are derived and computed using the elasto-hydrodynamic equations for quasicrystals. For the computation of the wavenumber and group speeds, we use Fourier transform approximation of the phonon and the phason displacement modes. The characteristic equations obtained are a polynomial equation of the wavenumber (k(n)), with frequency as a parameter. The corresponding group speeds (c(g)) for different frequencies are then computed from the wavenumber k(n). The variation of wavenumber and group speeds with frequency is plotted for the 1-D quasicrystal, 2-D decagonal Al-Ni-Co quasicrystals, and 3-D icosahedral Al-Pd-Mn and Zn-Mg-Sc quasicrystals. From the wavenumber and group speeds plots, we obtain the cut-off frequencies for different spatial wavenumber eta(m). The results show that for 1-D, 2-D, and 3-D quasicrystals, the phonon displacement modes are non-dispersive for low values of eta(m) and becomes dispersive for increasing values of eta(m). The cut-off frequencies are not observed for very low values of eta(m), whereas the cut-off frequency starts to appear with increasing eta(m). The group speeds of the phason displacement modes are orders of magnitude lower than that of the phonon displacement modes, showing that the phason modes do not propagate, and they are essentially the diffusive modes. The group speeds of the phason modes are also not influenced by eta(m). The group speeds for the 2-D quasicrystal at 35 kHz is also simulated numerically using Galerkin spectral finite element methods in frequency domain and is compared with the results obtained using wave propagation analysis. The effect of the phonon and phason elastic constants on the group speeds is studied using 3-D icosahedral Al-Pd-Mn and Zn-Mg-Sc quasicrystals. It is also shown that the phason elastic constants and the coupling coefficient do not affect the group speeds of the phonon displacement modes. (C) 2015 AIP Publishing LLC.

Doping effect of Ag+, Mn2+ ions on Structural and Optical Properties of ZnO nanoparticles

Pure ZnO and co-doped (Mn, Ag) ZnO nanoparticles have been successfully prepared by chemical co-precipitation method without using a capping agent. X-ray diffraction (XRD) studies confirms the presence of wurtzite (hexagonal) crystal structure similar to undoped ZnO, suggesting that doped Mn, Ag ions are substituted to the regular Zn sites. The morphology of the samples were studied by scanning electron microscopy (SEM). The chemical composition of pure and co-doped ZnO nanoparticles were characterized by energy dispersive X-ray analysis spectroscopy (EDAX). Optical absorption properties were determined by UV-vis Diffuse Reflectance Spectrophotometer. The incorporation of Ag+, Mn2+ in the place of Zn2+ provoked to decrease the size of nanocrystals as compared to pure ZnO. Optical absorption measurements indicates blue shift in the absorption band edge upon Ag, Mn ions doped ZnO nanoparticles.

Investigations on doping induced changes in structural, electronic structure and magnetic behavior of spintronic Cr-ZnS nanoparticles

Dilute magnetic semiconducting Zn1-xCrxS (x = 0.00, 0.01, 0.03, 0.05, 0.07) nanoparticles were synthesized by the co-precipitation technique using thioglycerol as the capping agent. Powder X-ray diffraction studies showed that Zn1-xCrxS nanoparticles exhibit zinc blende structure with no secondary phase, indicating that Cr ions are substituted at the Zn sites. Photoluminescence and Raman studies show the incorporation of Cr in ZnS nanoparticles. X-ray absorption studies depict that the valence of Zn remains unchanged and maintained in the divalent state, upon doping with Cr. The M-H curves at room temperature indicate the presence of weak ferromagnetism at room temperature due to structural defects. The increase in ferromagnetism with increasing Cr content up to 3%, demonstrates the possibility of tailoring the weak ferromagnetism in ZnS by appropriate Cr doping. (C) 2015 Elsevier Ltd. All rights reserved.

New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

The X-ray photoelectron spectroscopy and high-temperature structural studies of Zn1-xNixO/NiO two-phase composites

Detailed investigation of the chemical states and local atomic environment of Ni and Zn in the two-phase composites of Zn1-xNixO/NiO was reported. The X-ray photoelectron spectra of both Ni-2p and Zn-2p revealed the existence of a doublet with spin-orbit splitting approximate to 17.9 and 23.2eV, respectively confirming the divalent oxidation state of both Ni and Zn. However, the samples fabricated under oxygen-rich conditions exhibit significant difference in the binding energy approximate to 18.75eV between the 2p3/2 and 2p1/2 states of Ni. The shift in the satellite peaks of Ni-2p with increasing the Ni composition x within the Zn1-xNixO/NiO matrix signifies the attenuation of nonlocal screening because of reduced site occupancy of two adjacent Zn ions. The temperature dependence of X-ray diffraction analysis reveals a large distortion in the axial-rhombohedral angle for oxygen-rich NiO. Conversely, no significant distortion was noticed in the NiO system present as a secondary phase within Zn1-xNixO. Nevertheless, the unit-cell volume of both wurtzite h.c.p. Zn1-xNixO and f.c.c. NiO exhibits an anomalous behavior between 150 and 300 degrees C. The origin of such unusual change in the unit-cell volume was discussed in terms of oxygen stoichiometry.

Isotopic and geochemical characterization of invader tilapia fishes from water bodies of West Bengal and Karnataka, India

The otoliths (N = 12) of freshwater invasive species tilapia (Tilapia mossambicus) collected from two water bodies located at Kolkata and Bangalore, India, were analyzed for stable isotopes (delta 18O, delta 14C) and major and trace elements in order to assess the suitability of using otoliths as a tracer of aquatic environmental changes. The stable isotope analysis was done using the dual inlet system of a Finnigan-MAT 253 isotope ratio mass spectrometer (Thermo-Fisher, Bremen, Germany). Concentrations of major and trace elements were determined using a Thermo X-Series II quadrupole mass spectrometer. The stable isotope composition in tilapia otolith samples from Bangalore and Kolkata water bodies are quite good agreeing with that of the respective lake/pond and rain water. Elemental composition revealed in a pattern of Ca > Fe > Na > Sr > K > Ba > Cr > Mg > As > Mn > Zn > Co > Cu > Cd > Pb. The otoliths from Kolkata pond water are more enriched in Ba, Zn, Pb, Mn, Se, Cu, Zn, Cd, and Ni whereas Cr and As were found to be higher in otolith samples from Bangalore lake. The enrichment factor (EF) values of Cr were higher for both the sampling location in comparison with other metals, although all the studied metals exhibited EF values >1. The PCA shows clustering of metals in the otolith which are related either with the metabolic and physiological attributes or waterborne source. The study demonstrated the potential of stable isotope techniques to distinguish otolith specimens from varied climatic zone, while elemental composition recorded the quality of water at both the locations. The role of climate driving the quality of water can be understood by detailed and continuous monitoring of otolith specimens in the future. Future method allows reconstruction of climate and water quality from old specimens from field exposures or museum collection.

Magnetic properties of nanocrystalline Mn1-xZnxFe2O4

Nanocrystalline Mn1-xZnxFe2O4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0) were prepared via solution combustion method. Structural and morphology of Mn-Zn ferrites were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). Magnetic properties were carried out using vibrating sample magnetometer (VSM) at room temperature (RT) up to maximum field of 1.5 T. The room temperature real and imaginary part of permeability(mu' and mu'') has been measured in the frequency range of 1MHz to 1GHz. The room temperature XRD patterns exhibits the spinel cubic (Fm-3m) structure and broad XRD patterns shows the presence of nanoparticles. The imaginary part of the permeability (mu'') gradually increased with the frequency and took a broad maximum at a certain frequency, where the real permeability (mu') rapidly decreases, which is known as natural resonance. The coercive filed values are low, hence probability of domain rotation is also lower and the magnetization decreased with zinc substitution. The values of mu' and mu'' increases sharply, attained a maximum and then decreases with zinc content.

Development of an automated ultrasonic spray pyrolysis system and the growth of Cu2ZnSnS4 thin films

An automated ultrasonic spray pyrolysis system is fabricated for the growth of thin films. The system is equipped with x-y movement and enables film deposition in different patterns and spray rates. Cu-2(Zn,Sn)S-4 (CZTS) films are deposited using this setup. The substrate temperature (T-s) is varied from 240 to 490 degrees C. Kesterite CZTS phase is observed in all the films together with binary phases. The films prepared at T-s <340 degrees C showed SnxSy phase and those at T-s >340 degrees C showed Cu2S phase. Sulfur incorporation is maximum (40%) at 440 degrees C and the films showed better morphology. The Cu and S concentrations are varied to remove binary phases. Depth wise elemental analysis confirmed the existence of single phase CZTS. p-Type CZTS films of resistivity in the range of 10(2)-10(3) Omega cm are obtained. (C) 2015 Elsevier B.V. All rights reserved.

Investigations on structural, magnetic and electronic structure of Gd-doped ZnO nanostructures synthesized using sol-gel technique

GdxZn1-xO (x = 0, 0.02, 0.04 and 0.06) nanostructures have been synthesized using sol-gel technique and characterized to understand their structural and magnetic properties. X-ray diffraction (XRD) results show that Gd (0, 2, 4 and 6 %)-doped ZnO nanostructures crystallized in the wurtzite structure having space group C3(v) (P6(3)mc). Photoluminescence and Raman studies of Gd-doped ZnO powder show the formation of singly ionized oxygen vacancies. X-ray absorption spectroscopy reveals that Gd replaces the Zn atoms in the host lattice and maintains the crystal symmetry with slight lattice distortion. Gd L-3-edge spectra reveal charge transfer between Zn and Gd dopant ions. O K-edge spectra also depict the charge transfer through the oxygen bridge (Gd-O-Zn). Weak magnetic ordering is observed in all Gd-doped ZnO samples.

Thermoelectric Properties of In-Doped Cu2ZnGeSe4

Recently, much research has been focused on finding new thermoelectric materials. Cu-based quaternary chalcogenides that belong to A(2)BCD(4) (A = Cu; B = Zn, Cd; C = Sn, Ge; D = S, Se, Te) are wide band gap materials and one of the potential thermoelectric materials due to their complex crystal structures. In this study, In-doped quaternary compounds Cu2ZnGe1-xInxSe4 (x = 0, 0.025, 0.05, 0.075, 0.1) were prepared by a solid state synthesis method. Powder x-ray diffraction patterns of all the samples showed a tetragonal crystal structure (space group I-42m) of the main phase with a trace amount of impurity phases, which was further confirmed by Rietveld analysis. The elemental composition of all the samples showed a slight deviation from the nominal composition with the presence of secondary phases. All the transport properties were measured in the temperature range 373-673 K. The electrical resistivity of all the samples initially decreased up to similar to 470 K and then increased with increase in temperature upto 673 K, indicating the transition from semiconducting to metallic behavior. Positive Seebeck coefficients for all the samples revealed that holes are the majority carriers in the entire temperature range. The substitution of In3+ on Ge4+ introduces holes and results in the decrease of resistivity as well as the Seebeck coefficient, thereby leading to the optimization of the power factor. The lattice thermal conductivity of all the samples decreased with increasing temperature, indicating the presence of phonon-phonon scattering. As a result, the thermoelectric figure of merit (zT) of the doped sample showed an increase as compared to the undoped compound.

Interpenetrated and Catenated Zinc Thiosulfates Frameworks with dia and qtz Nets: Synthesis, Structure, and Properties

Reactions between Zn(NO3)(2)center dot 6H(2)O, Na2S2O3, 4,4'-bipyridine (bpy), 1,2-bis(4-pyridyl)ethene (bpe), 1,2-bis (4-pyridyl) ethane (bpa), and 1,3-bis(4-pyridyl)propane (bpp) under solvothermal conditions resulted in four new zinc thiosulfate hybrid compounds. Compound I has four-membered zinc thiosulfate rings connected by the ligand, 1,3-bis(4-pyridyl)propane (bpp) forming a two-dimensional structure. Compounds II-IV have one-dimensional zinc thiosulfate chains connected by the ligands, bpy (II), bpe (III), and bpa (IV) giving rise to three-dimensional structures. All the four-structures exhibit 3-fold interpenetration. Proton conductivity studies indicate reasonable proton mobility at 34 degrees C and at 98% relative humidity. The compounds also exhibit Lewis acid character and good photocatalytic activity for the decomposition of cationic dyes.

Enhanced photocatalytic activity of ultra-high aspect ratio ZnO nanowires due to Cu induced defects

We report the synthesis of ZnO nanowires in ambient air at 650 degrees C by a single-step vapor transport method using two different sources Zn (ZnO nanowires-I) and Zn:Cu (ZnO nanowires-II). The Zn:Cu mixed source co-vaporize Zn with a small amount of Cu at temperatures where elemental Cu source does not vaporize. This method provides us a facile route for Cu doping into ZnO. The aspect ratio of the grown ZnO nanowires-II was found to be higher by more than five times compared ZnO nanowires-I. Photocatalytic activity was measured by using a solar simulator and its ultraviolet-filtered light. The ZnO nanowires-II shows higher catalytic activity due to increased aspect ratio and higher content of surface defects because of incorporation of Cu impurities.

Productividad y concentración de nutrientes del Taiwán Cubano (Pennisetum purpureum X Pennisetum tiphoides), CT 115, en época lluviosa, 2010 en la Fincas Santa Rosa

Con el objetivo de evaluar la Productividad y concentración de nutrientes del pasto cubano (Pennisetum purpureum x Pennisetum typhoides) cv CT – 115, se llevó a cabo la presente investigación en la finca Santa Rosa propiedad de la Universidad Nacional Agraria (UNA) Managua, Nicaragua. Localizada geográficamente a los 12° 08´ 33"de latitud norte y, 86° 10´ 31" de longitud oeste (INETER, 2006). Para ello se utilizó un área total de 33 m2 la cual se subdividió en tres parcelas de 10 m2 cada una donde se realizaron cortes cada 15 días hasta llegar a los 75 días. Se evaluaron las variables : altura, (cm) biomasa fresca (kg ha-1), Materia Seca (%), Biomasa seca (kg ha-1), Nitrógeno (%), Fósforo (%), Potasio (%),Calcio (%), Magnesio (%), Hierro (ppm), Manganeso (ppm), Zinc (ppm). Para la determinación de la producción de biomasa verde y seca (kg ha-1), se utilizó la metodología propuesta por la Red Internacional de evaluación de Pasturas Tropicales (CIAT, 1982). Para determinar los parámetros MS (%) se utilizó la metodología del análisis de Weende o análisis proximal (AOAC. 1990). Para el análisis de correlación se utilizo el programa SAS VERSION 9 para cada uno de las variables evaluadas, para la determinación de las curvas de mejor ajuste se utilizó el programa CVXP32. Durante el ensayo no se aplico ningún tipo de tratamiento agronómico (fertilización, riego). Los resultados obtenidos fueron: Altura 220 cm Biomasa fresca 31,764 kg ha-1 Materia seca 24% Biomasa seca 7529 kg ha-1. Las mayores concentraciones de nutrientes en la planta fueron: N 3.21% P 0.38% K 4.94% Ca 0.24% Mg 0.18% Fe 105.0ppm Mn 53.33ppm Zn 50ppm. Los modelos de mejor ajuste son: Modelo Múltiple Multiplicativo, Modelo Richards, Modelo Harris, Función Rotacional, Tercer Grado Polinomial y Asociación Exponencial.

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.