Metal-complex ionosilicas: Cationic mesoporus silica with Ni(II) and Cu(II) complexes in their framework

Metal-complex ionosilicas with cationic complexes into the mesoporous silica framework were prepared using anionic surfactants. The electrostatic interaction between the anionic surfactant and the cationic metal complexes incorporated in the silica framework allows for the fine tuning of the mesoporous structure. The gentle procedure of synthesis developed and mild ion-exchange extraction of the surfactant, allowed a cleaner route for the immobilization of homogeneous cationic catalysts in mesoporous silica, while protecting the structural and chemical integrity of the metal complexes.

Figure 5. Trace metal analysis of sediment core PS1506-1

An increase in whole ocean alkalinity during glacial periods could account, in part, for the drawdown of atmospheric CO2 into the ocean. Such an increase was inevitable due to the near elimination of shelf area for the burial of coral reef alkalinity. We present evidence, based on down-core measurements of benthic foraminiferal B/Ca and Mg/Ca from a core in the Weddell Sea, that the deep ocean carbonate ion concentration, [CO3 2-], was elevated by ~25 µmol/kg during each glacial period of the last 800 kyrs. The heterogeneity of the preservation histories in the different ocean basins reflects control of the carbonate chemistry of the deep glacial ocean in the Atlantic and Pacific by the changing ventilation and chemistry of Weddell Sea waters. These waters are more corrosive than interglacial northern sourced waters, but not as undersaturated as interglacial southern sourced waters. Our inferred increase in whole ocean alkalinity can be reconciled with reconstructions of glacial saturation horizon depth and the carbonate budget, if carbonate burial rates also increased above the saturation horizon as a result of enhanced pelagic calcification. The Weddell records display low [CO3 2-] during deglaciations and peak interglacial warmth, coincident with maxima in %CaCO3 in the Atlantic and Pacific Oceans. Should the burial rate of alkalinity in the more alkaline glacial deepwaters outstrip the rate of alkalinity supply, then pelagic carbonate production by the coccolithophores, at the end of the glacial maximum could drive a decrease in ocean [CO3 2-] and act to trigger the deglacial rise in pCO2.

Dynamic annealing in III-nitrides under ion bombardment

We study the evolution of structural defects in AlxGa1-xN films (with x=0.0-0.6) bombarded with kilo-electron-volt heavy ions at 77 and 300 K. We use a combination of Rutherford backscattering/channeling spectrometry and cross-sectional transmission electron microscopy. Results show that an increase in Al content not only strongly enhances dynamic annealing processes but can also change the main features of the amorphization behavior. In particular, the damage buildup behavior at 300 K is essentially similar for all the AlGaN films studied. Ion-beam-produced disorder at 300 K accumulates preferentially in the crystal bulk region up to a certain saturation level (similar to50%-60% relative disorder). Bombardment at 300 K above a critical fluence results in a rapid increase in damage from the saturation level up to complete disordering, with a buried amorphous layer nucleating in the crystal bulk. However, at 77 K, the saturation effect of lattice disorder in the bulk occurs only for xgreater than or similar to0.1. Based on the analysis of these results for AlGaN and previously reported data for InGaN, we discuss physical mechanisms of the susceptibility of group-III nitrides to ion-beam-induced disordering and to the crystalline-to-amorphous phase transition. (C) 2004 American Institute of Physics.

Structural, electrical, and optical analysis of ion implanted semi-insulating InP

Semi-insulating InP was implanted with MeV P, As, Ga, and In ions, and the resulting evolution of structural properties with increased annealing temperature was analyzed using double crystal x-ray diffractometry and cross sectional transmission electron microscopy. The types of damage identified are correlated with scanning spreading resistance and scanning capacitance measurements, as well as with previously measured Hall effect and time resolved photoluminescence results. We have identified multiple layers of conductivity in the samples which occur due to the nonuniform damage profile of a single implant. Our structural studies have shown that the amount and type of damage caused by implantation does not scale with implant ion atomic mass. (C) 2004 American Institute of Physics.

Metal Clips Induce Folding of a Short Unstructured Peptide into an a-Helix via Turn Conformations in Water. Kinetic versus Thermodynamic Products

Short peptides corresponding to two to four a-helical turns of proteins are not thermodynamically stable helices in water. Unstructured octapeptide Ac-His1*-Ala2-Ala3-His4*-His5*-Glu6-Leu7-His8*-NH2 (1) reacts with two [Pd ((NH2)-N-15(CH2)(2) (NH2)-N-15)(NO3)(2)] in water to form a kinetically stable intermediate, [{Pden}(2)-{(1,4)(5,8)-peptide}](2), in which two 19-membered metallocyclic rings stabilize two peptide turns. Slow subsequent folding to a thermodynamically more stable two-turn a-helix drives the equilibrium to [{Pden}(2)-{(1,5)(4,8)-peptide}] (3), featuring two 22-membered rings. This transformation from unstructured peptide via turns to an a-helix suggests that metal clips might be useful probes for investigating peptide folding.

Are metal ions accumulated by saxicolous lichens growing in a rural environment?

The levels of Mn, Cu, zn, Mg and Ca were measured in the lichens Xanthoparmelia conspersa (Ach.) Hale and Parmelia glabratula ssp. fuliginosa (Fr. ex Duby): Laund. growing on a steep slate rock surface in south Gwynedd, Wales, UK. The objective was to test the following hypotheses: 1) that foliose lichens growing in a rural environment concentrate metal ions relative to the substratum, 2) that the concentration of metal ions increases significantly with thallus size and 3) that individual ions accumulate preferentially either in the marginal lobes or thallus centre. Mg and Ca were present in rainfall whereas all ions were present in rock surface runoff and in the substratum. Levels of Mn, Mg and Ca were increased in runoff collected from the bottom compared with the top of the rock surface. In P. glabratula ssp. fuliginosa thalli, ions were present as follows, Mg > Ca=Mn=Zn>Cu, and there were no significant differences in thalli collected from the top and bottom of the rock surface. With the exception of Mg and Ca, ion levels in thalli were similar to or less than those in the substratum. The levels of Ca, Cu and Zn were similar in thalli from under 1 to over 4 cm in diameter. However, the level of Mg increased with thallus size in X. conspersa while the level of Mn decreased with thallus size in both species. Ion levels were similar in the marginal lobes and centres of large diameter (over 4 cm) and small diameter (under 2 cm) X. conspersa thalli. With the exception of Mg, there was no evidence for a significant accumulation of ions relative to the substratum or with thallus size. In addition, there was no evidence to suggest preferential accumulation of ions either in the thallus centre or marginal lobes.

Effect of sample preparation on the thermal degradation of metal-added biomass

The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical-chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material. © 2011 Elsevier B.V. All rights reserved.

The characterisation of clean metal surfaces

The most perfectly structured metal surface observed in practice is that of a field evaporated field-ion microscope specimen. This surface has been characterised by adopting various optical analogue techniques. Hence a relationship has been determined between the structure of a single plane on the surface of a field-ion emitter and the geometry of a binary zone plate. By relating the known focussing properties of such a zone plate to those obtained from the projected images of such planes in a field-ion micrograph, it is possible to extract new information regarding the local magnification of the image. Further to this, it has been shown that the entire system of planes comprising the field-ion imaging surface may be regarded as a moire pattern formed between over-lapping zone plates. The properties of such moire zone plates are first established in an analysis of the moire pattern formed between zone plates on a flat surface. When these ideas are applied to the field-ion image it becomes possible to deduce further information regarding the precise topography of the emitter. It has also become possible to simulate differently proJected field-ion images by overlapping suitably aberrated zone plates. Low-energy ion bombardment is an essential preliminary to much surface research as a means of producing chemically clean surfaces. Hence it is important to know the nature and distribution of the resultant lattice damage, and the extent to which it may be removed by annealing. The field-ion microscope has been used to investigate such damage because its characterisation lies on the atomic scale. The present study is concerned with the in situ sputtering of tungsten emitters using helium, neon, argon and xenon ions with energies in the range 100eV to 1keV, together with observations of the effect of annealing. The relevance of these results to surface cleaning schedules is discussed.

Interrogation of a sonogashira cross-coupling of 8-bromoguanosine with phenylacetylene on amberlite:evidence for Pd/Cu ion binding and propagation of Pd/Cu nanoparticles

The reactivity of Amberlite (IRA-67) base "heterogeneous" resin in Sonogashira cross-coupling of 8-bromoguanosine 1 with phenylacetylene 3 to give 2 has been examined. Both 1 and 2 coordinate to Pd and Cu ions, which explains why at equivalent catalyst loadings, the homogeneous reaction employing triethylamine base is poor yielding. X-ray photo-electron spectroscopy (XPS) has been used to probe and quantify the active nitrogen base sites of the Amberlite resin, and postreaction Pd and Cu species. The Pd2Cl3(PPh)2 precatalyst and CuI cocatalyst degrade to give Amberlite-supported metal nanoparticles (average size ∼2.7 nm). The guanosine product 2 formed using the Amberlite Pd/Cu catalyst system is of higher purity than reactions using a homogeneous Pd precatalyst, a prerequisite for use in biological applications. Copyright © Taylor and Francis Group, LLC.

Heavy ion irradiation effects in zirconium nitride

Polycrystalline zirconium nitride (ZrN) samples were irradiated with He +, Kr ++, and Xe ++ ions to high (>1·10 16 ions/cm 2) fluences at ∼100 K. Following ion irradiation, transmission electron microscopy (TEM) and grazing incidence X-ray diffraction (GIXRD) were used to analyze the microstructure and crystal structure of the post-irradiated material. For ion doses equivalent to approximately 200 displacements per atom (dpa), ZrN was found to resist any amorphization transformation, based on TEM observations. At very high displacement damage doses, GIXRD measurements revealed tetragonal splitting of some of the diffraction maxima (maxima which are associated with cubic ZrN prior to irradiation). In addition to TEM and GIXRD, mechanical property changes were characterized using nanoindentation. Nanoindentation revealed no change in elastic modulus of ZrN with increasing ion dose, while the hardness of the irradiated ZrN was found to increase significantly with ion dose. Finally, He + ion implanted ZrN samples were annealed to examine He gas retention properties of ZrN as a function of annealing temperature. He gas release was measured using a residual gas analysis (RGA) spectrometer. RGA measurements were performed on He-implanted ZrN samples and on ZrN samples that had also been irradiated with Xe ++ ions, in order to introduce high levels of displacive radiation damage into the matrix. He evolution studies revealed that ZrN samples with high levels of displacement damage due to Xe implantation, show a lower temperature threshold for He release than do pristine ZrN samples.

Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex

Materials that combine photoluminescence, optical transparency and facile processability are of high importance in many applications. This article reports on the development of photoluminescent poly(methyl methacrylate) materials based on novel highly emissive anionic molybdenum cluster complex [{Mo6I8}(OTs)6]2– (where OTs– is the p-toluenesulfonate ion). The materials were obtained by both solution and bulk copolymerisation of methyl methacrylate and (dMDAEMA)2[{Mo6I8}(OTs)6], where dMDAEMA+ is the polymerisable cation [2-(methacryloyloxy)ethyl]dimethyl-dodecylammonium. Evaluation of the resultant hybrid materials showed that one could combine the excellent photoluminescent properties of the cluster complex with the transparency and processability of PMMA.

Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Mineralogy, mineral chemistry, and genesis of precious metal-bearing volcanogenic massive sulfide deposits in the Newfoundland Appalachians, Canada: the Ming deposit as example

The Ming deposit, Newfoundland Appalachians, is a metamorphosed (upper greenschist to lower amphibolite facies), Cambro-Ordovician, bimodalmafic volcanogenic massive sulfide (VMS) deposit that consists of several, spatially-associated, elongated orebodies composed of stratabound semimassive to massive sulfides and/or discordant sulfide stringers in a rhyodacitic footwall. Copper is the main commodity; however, the deposit contains precious metal-bearing zones with elevated Au grades. In this study, field observations, microscopy, and micro-analytical tools including electron microprobe, laser ablation inductively coupled plasma mass spectrometry, and secondary ion mass spectrometry were used to constrain the relative timing of precious metal emplacement, the physico-chemical conditions of hydrothermal fluid precipitation, and the sources of sulfur, precious metals, semi-metals and metals. The ore mineral assemblage is complex and indicates an intermediate sulfidation state. Pyrite and chalcopyrite are the dominant ore minerals with minor sphalerite and pyrrhotite, and trace galena, arsenopyrite and cubanite. Additional trace phases include tellurides, NiSb phases, sulfosalts, electrum, AgHg±Au alloys, and oxides. Silver phases and precious metals occur predominantly in semi-massive and massive sulfides as free grains, and as grains spatially associated with arsenopyrite and/or sulfosalts. Precious metal phases occurring between recrystallized pyrite and within cataclastic pyrite are rare. Hence, the complex ore assemblage and textures strongly suggest syngenetic precious metal emplacement, whereas metamorphism and deformation only internally and locally remobilized precious metal phases. The ore assemblage formed from reduced, acidic hydrothermal fluids over a range of temperatures (≈350 to below 260ºC). The abundance of telluride and Ag-bearing tetrahedrite, however, varies strongly between the different orebodies indicating variable ƒTe₂, ƒSe₂, mBi, and mSb within the hydrothermal fluids. The variations in the concentrations of semi-metals and metals (As, Bi, Hg, Sb, Se, Te), as well as Au and Ag, were due to variations in temperature but also to a likely contribution of magmatic fluids into the VMS hydrothermal system from presumably different geothermal reservoirs. Sulfur isotope studies indicate at least two sulfur sources: sulfur from thermochemically-reduced seawater sulfate and igneous sulfur. The source of igneous sulfur is the igneous footwall, direct magmatic fluid/volatiles, or both. Upper greenschist to lower amphibolite metamorphic conditions and deformation had no significant effect on the sulfur isotope composition of the sulfides at the Ming deposit.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials

Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.