Lead-germanate glasses and fibers: A practical alternative to tellurite for nonlinear fiber applications

We report on the fabrication of novel lead-germanate glasses and fibers. We have characterized these glasses in terms of their thermal properties, Raman spectra and refractive indices (both linear and nonlinear) and present them as viable alternatives to tellurite glasses for applications requiring highly nonlinear optical fibers. © 2013 Optical Society of America.

Zinc, cadmium and lead resistance mechanisms in bacteria and their contribution to biosensing

In bacteria resistance to heavy metals is mainly achieved through active efflux, but also sequestration with proteins or as insoluble compounds is used. Although numerous studies have dealt with zinc, cadmium and lead resistance mechanisms in bacteria, it has still remained unclear how different transporters are integrated into an effective homeostasis/resistance network and whether specific mechanisms for lead sequestration exist. Furthermore, since metals are toxic not only to bacteria but to higher organisms as well, it is important to be able to estimate possible biological effects of heavy metals in the environment. This could be done by determining the bioavailable amount of the metals in the environment with bacterial bioreporters. That is, one can employ bacteria that respond to metal contamination by a measurable signal to assess the property of metals to cross biological membranes and to cause harmful effects in a possibly polluted environment. In this thesis a new lead resistance mechanism is described, interplay between CBA transporters and P-type ATPases in zinc and cadmium resistance is presented and finally the acquired knowledge is used to construct bacterial bioreporters for heavy metals with increased sensitivity and specificity. The new lead resistance model employs a P-type ATPase that removes Pb2+ ions from the cytoplasm and a phosphatase that produces inorganic phosphate for lead sequestration in the periplasm. This was the first study where the molecular mechanism of lead sequestration has been described. Characterization of two P-type ATPases and two CBA transporters showed that resistance mechanisms for Zn2+ and Cd2+ are somewhat different than for Pb2+ as these metals cannot be sequestered as insoluble compounds as easily. Resistance to Zn2+ was conferred merely by the CBA transporter that could export both cytoplasmic and periplasmic ions; whereas, full resistance to Cd2+ required interplay of a P-type ATPase that exported cytoplasmic ions to periplasm and a CBA transporter that further exported periplasmic ions to the outside. The knowledge on functionality of the transporters and metal-inducible promoters was exploited in bioreporter technology. A transporter-deficient bioreporter strain that lacked exporters for Zn2+/Cd2+/Pb2+ could detect up to 45-fold lower metal concentrations than its wild type counterpart due to the accumulation of metals in the cell. The broad specificity issue of bioreporters was overcome by using Zn-specific promoter as a sensor element, thus achieving Zn-specific bioreporter.

In-situ one-step hydrothermal synthesis of a lead germanate-graphene composite as a novel anode material for lithium-ion batteries

Lead germanate-graphene nanosheets (PbGeO3-GNS) composites have been prepared by an efficient one-step, in-situ hydrothermal method and were used as anode materials for Li-ion batteries (LIBs). The PbGeO3 nanowires, around 100–200 nm in diameter, are highly encapsulated in a graphene matrix. The lithiation and de-lithiation reaction mechanisms of the PbGeO3 anode during the charge-discharge processes have been investigated by X-ray diffraction and electrochemical characterization. Compared with pure PbGeO3 anode, dramatic improvements in the electrochemical performance of the composite anodes have been obtained. In the voltage window of 0.01–1.50 V, the composite anode with 20 wt.% GNS delivers a discharge capacity of 607 mAh g−1 at 100 mA g−1 after 50 cycles. Even at a high current density of 1600 mA g−1, a capacity of 406 mAh g−1 can be achieved. Therefore, the PbGeO3-GNS composite can be considered as a potential anode material for lithium ion batteries.

Simultaneous effect of lead and cadmium on granulosa cells: A cellular model for ovarian toxicity

Lead (Pb) and cadmium (Cd) are known reproductive toxicants, which accumulate in granulosa cells of the ovary. Female Charles foster rats were treated with sodium acetate (control), lead acetate and cadmium acetate either alone or in combination at a dose 0.05 mg/kg body weight intra-peritoneally for 15 days daily. Animals were killed at proestrous stage and granulosa cells were isolated from the ovaries. Binding of I-125-luteinizing hormone (I-125-LH), I-125-follicle stimulating hormone (I-125-FSH) and 17 beta-hydroxysteroid dehydrogenase activity were measured. As these receptors are localized on the surface of the cell membrane, we also estimated the membrane parameters of these cells. Our results demonstrated that both lead and cadmium caused a significant reduction in gonadotropin binding, which altered steroidogenic enzyme activity of granulosa cells. These changes exhibited a positive correlation with membrane changes of the granulosa cells.

Formation of lead pyrophosphate glass and the role of anion disproportionation

Thermal, spectroscopic and electrical properties of lead pyrophosphate glass prepared by melt quenching have been examined. A model based on the structural disproportionation of the P2O 7 4− ions has been proposed and is shown to consistently explain all the observations. The equilibrium of various anionic species has been discussed on the basis of their electronegativities which are in turn related to their basicities.

Chemically functionalized glassy carbon spheres: a new covalent bulk modified composite electrode for the simultaneous determination of lead and cadmium

A new type of covalent bulk modified glassy carbon composite electrode has been fabricated and utilized in the simultaneous determination of lead and cadmium ions in aqueous medium. The covalent bulk modification was achieved by the chemical reduction of 2-hydroxybenzoic acid diazonium tetrafluroborate in the presence of hypophosphorous acid as a chemical reducing agent. The covalent attachment of the modifier molecule was examined by studying Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and the surface morphology was examined by scanning electron microscopy images. The electrochemistry of modified glassy carbon spheres was studied by its cyclic voltammetry to decipher the complexing ability of the modifier molecules towards Pb2+ and Cd2+ ions. The developed sensor showed a linear response in the concentration range 1-10 mu M with a detection limit of 0.18 and 0.20 mu M for lead and cadmium, respectively. The applicability of the proposed sensor has been checked by measuring the lead and cadmium levels quantitatively from sewage water and battery effluent samples.

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

Intense frequency upconversion luminescence in Yb3+/Tm3+-codoped oxychloride germanate glasses

Yb3+/Tm3+-codoped oxychloride germanate glasses for developing potential upconversion lasers have been fabricated and characterized. Structural properties were obtained based on the Raman spectra analysis, indicating that PbCl2 plays an important role in the formation of glass network and has an important influence on the maximum phonon energies of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4), respectively, were observed at room temperature. With increasing PbCl2 content, the intensity of blue (477 nm) emission increases significantly, while the red (650 nm) emission increases slowly. The results indicate that PbCl2 has more influence on the blue emissions than the red emission in oxychloride germanate glasses. The possible upconversion mechanisms are discussed and estimated. Intense blue upconversion luminescence indicates that these oxychloride germanate glasses can be used as potential host material for upconversion lasers. C (c) 2005 Springer Science + Business Media, Inc.

Efficient frequency upconversion emission in Er3+-doped novel strontium lead bismuth glass

Er3+ -doped strontium lead bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(1) (t = 2,4,6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 2.95 x 10(-20), Omega(4) = 0-91 X 10(-20), and Omega(6) = 0.36 x 10(-20) cm(2). Under 975 nm excitation, intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) --> I-4(15/2), S-4(3/2) I-4(15/2), and F-4(9/2) --> I-4(15/2) respectively were observed. The upconversion mechanisms are discussed based oil the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for the green and red emissions. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. (C) 2004 Published by Elsevier B.V.

Effect of chloride ions' introduction on structural, thermal stability, and spectroscopic properties in Yb3+Er3+-codoped germanate-bismuth-lead glasses

Yb3+Er3+-codoped chloride-modified germanate-bismuth-lead glasses have been synthesized by the conventional melting and quenching method. Structural and thermal stability properties have been obtained on the basis of the Raman spectra and differential thermal analysis, which indicate that the PbCl2 addition has an important influence on the phonon density of states, maximum phonon energy, and thermal stability of host glasses. The Judd-Ofelt intensity parameters and quantum efficiencies were calculated on the basis of the Judd-Ofelt theory and lifetime measurements. For the 1.53 mu m emission band, the full widths at the half-maximum increase and peak wavelengths are blueshifted with increasing PbCl2 content. Moreover, the effect of the PbCl2 addition on the phonon density of states, OH- content, and upconversion luminescence has been discussed and evaluated. Our results reveal that, with increasing PbCl2 content, the decrease of phonon density and OH- content contributes more to the enhanced upconversion emissions than that of maximum phonon energy. (c) 2005 Optical Society of America

Infrared-to-visible upconversion fluorescence of Er3+-doped novel lithium-barium-lead-bismuth glass

Er3+-doped lithium-barium-lead-bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(t) (t = 2, 4, 6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 3.05 x 10(-20) cm(2), Omega(4) = 0.95 x 10(-20) cm(2), and Omega(6) = 0.39 x 10(-20) cm(2). Under 975 nm excitation, intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were observed at room temperature. The upconversion mechanisms are discussed based on the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for the green and red emissions. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the intense upconversion processes. The intense upconversion luminescence of Er3+-doped lithium-barium-lead-bismuth glass may be a potentially useful material for developing upconversion optical devices. (c) 2004 Elsevier B.V. All rights reserved.

Structural and upconversion fluorescence properties of Er3+/Yb3+-codoped lead-free germanium-bismuth glass

We study the structural and infrared-to-visible upconversion fluorescence properties of Er3(+)/Yb3+-codoped lead-free germanium-bismuth glass. The structure of lead-free germanium-bismuth-lanthanum glass is investigated by peak-deconvolution of Raman spectroscopy. Intense green and red emissions centred at 525, 546, and 657nm, corresponding to the transitions H-2(11/2) -> (IT15/2)-I-4 -> S-4(3/2) -> 4I(15/2), and F-4(9/2) -> I-4(15/2), respectively, are observed at room temperature. The quadratic dependence of the 525, 546, and 657nm emissions on excitation power indicates that a two-photon absorption process occurs under 975nm excitation.

Green and red upconversion luminescence in ytterbium-sensitized erbrium-doped novel lead-free germanium bismuth lanthanum glass

Structural and infrared-to-visible upconversion fluorescence properties in ytterbium-sensitized erbrium-doped novel lead-free germanium bismuth-lanthanum glass have been studied. The structure of lead-free germanium-bismuth-lanthanum glass was investigated by peak-deconvolution of Raman spectrum, and the structural information was obtained from the peak wavenumbers. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were observed at room temperature. The quadratic dependence of the 525, 546, and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm excitation. This novel lead-free germanium-bismuth-lanthanum glass with low maximum phonon energy (similar to 751 cm(-1)) can be used as potential host material for upconversion lasers. (c) 2005 Published by Elsevier B.V.