A viologen-based UV indicator and dosimeter

A UV indicator/dosimeter based on benzyl viologen (BV2+) encapsulated in polyvinyl alcohol (PVA) is described. Upon exposure to UV light, the BV2+/PVA film turns a striking purple colour due to the formation of the cation radical, BV center dot+. The usual oxygen sensitivity of BV center dot+ is significantly reduced due to the very low oxygen permeability of the encapsulating polymer, PVA. Exposure of a typical BV2+/PVA film, for a set amount of time, to UVB light with different UV indices produces different levels of BV center dot+, as measured by the absorbance of the film at 550 nm. A plot of the change in absorbance at this wavelength, Delta Abs(550), as a function of UV index, UVI, produces a linear calibration curve which allows the film to be used as a UVB indicator, and a similar procedure could be employed to allow it to be used as a solar UVI indicator. A typical BV2+/PVA film generates a significant, semi-permanent (stable for > 24 h) saturated purple colour (absorbance similar to 0.8-0.9) upon exposure to sunlight equivalent to a minimal erythemal dose associated with Caucasian skin, i.e. skin type II. The current drawbacks of the film and the possible future use of the BV2+/PVA film as a personal solar UV dosimeter for all skin types are briefly discussed.

In Situ Single-Crystal Diffraction Studies of the Structural Transition of Metal-Organic Framework Copper 5-Sulfoisophthalate, Cu-SIP-3

The flexibility of the metal-organic framework Cu-2(OH)(C8H3O7S)(H2O)center dot 2H(2)O (Cu-SIP-3) toward reversible single-crystal to single-crystal transformations is demonstrated using in situ diffraction methods at variable temperature. At temperatures below a dehydration-induced phase transition (T < 370 K) the structure is confirmed as being hydrated. In the temperature range where the transition takes place (370 K < T < 405 K) no discrete, sharp Bragg peaks can be seen in the single-crystal X-ray diffraction pattern, indicating significant loss of long-range order. At temperatures higher than 405 K, the Bragg peaks return and the structure can be refined as dehydrated Cu-SIP-3. The loss of guest water molecules can be followed at temperatures below the phase transition giving insight into the mechanism of the dehydration. Addition of nitric oxide gas to the material above the gating opening pressure of 275 mbar also leads to loss of Bragg scattering in the diffraction pattern.

Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework

Metal organic frameworks (MOFs) are among the most exciting materials discovered recently, attracting particular attention for their gas-adsorption and -storage properties. Certain MOFs show considerable structural flexibility in response to various stimuli. Although there are several examples of 'breathing' MOFs, in which structural changes occur without any bond breaking, examples of transformations in which several bonds are broken and made are much rarer. In this paper we demonstrate how a flexible MOF, Cu-2(OH)(C8H3O7S)(H2O)center dot 2H(2)O, can be synthesized by careful choice of the organic linker ligand. The flexibility can be controlled by addition of a supplementary coordinating molecule, which increases the thermal stability of the solid sufficiently for direct imaging with electron microscopy to be possible. We also demonstrate that the MOF shows unprecedented low-pressure selectivity towards nitric oxide through a coordination-driven gating mechanism. The chemical control over these behaviours offers new possibilities for the synthesis of MOFs with unusual and potentially exploitable properties.

Exceptional Behavior over the Whole Adsorption-Storage-Delivery Cycle for NO in Porous Metal Organic Frameworks

Two porous metal organic frameworks (MOFs), [M-2(C8H2O6)(H2O)(2)] center dot 8H(2)O (M = Co, Ni), perform exceptionally well for the adsorption, storage, and water-triggered delivery of the biologically important gas nitric oxide. Adsorption and powder X-ray diffraction studies indicate that each coordinatively unsaturated metal atom in the structure coordinates to one NO molecule. All of the stored gas is available for delivery even after the material has been stored for several months. The combination of extremely high adsorption capacity (similar to 7 mmol of NO/g of MOF) and good storage stability is ideal for the preparation of NO storage solids. However, most important is that the entire reservoir of stored gas is recoverable on contact with a simple trigger (moisture). The activity of the NO storage materials is proved in myography experiments showing that the NO-releasing MOFs cause relaxation of porcine arterial tissue.

Dichloridobis(picolinohydrazide)cadmium(II)

The title compound, [CdCl2(C6H7N3O)(2)], was obtained unintentionally as a product of an attempted reaction of CdCl2 center dot 2.5H(2)O and picolinic acid hydrazide, in order to obtain a cadmium(II) complex analogous to a 15-metallacrown-5 complex of the formula [MCu5L5]X-n, with M = a central metal ion, L = picolinic acid hydrazide and X = Cl- , but with cadmium the only metal present. The coordination geometry around the Cd-II atom can be considered as distorted octahedral, with two bidentate picolinic acid hydrazide ligands, each coordinating through their carbonyl O atom and amino N atom, and two chloride anions. In the crystal structure, intermolecular N-H center dot center dot center dot Cl and N-H center dot center dot center dot N hydrogen bonds link the molecules into a two-dimensional network parallel to the ( 100) plane. The pyridine rings of adjacent networks are involved in pi-pi stacking interactions, the minimum distance between the ring centroids being 3.693 (2) angstrom.

Di-mu-chloro-bis({2-[(2-hydroxyethyl)iminomethyl]phenolato-kappa N-3,O,O '} nickel(II)) methanol solvate

The title compound, [Ni2Cl2(C9H10NO2)(2)]center dot CH3OH, is a dinuclear unit built up by two nickel(II) complexes, bridged by two Cl atoms. The coordination geometry around each Ni-II atom can be considered as distorted square-pyramidal, with the tridendate chelate Schiff base ligands coordinating in a trans conformation through their imine N atom and phenoxy and alkoxy O atoms.

Magma Evolution in the Primitive, Intra-oceanic Tonga Arc: Petrogenesis of Basaltic Andesites at Tofua Volcano

Tofua volcano is situated midway along the Tonga oceanic arc and has undergone two phases of ignimbrite-forming activity. The eruptive products are almost entirely basaltic andesites (52 center dot 5-57 wt % SiO2) with the exception of a volumetrically minor pre-caldera dacite. The suite displays a strong tholeiitic trend with K2O <1 wt %. Phenocryst assemblages typically comprise plagioclase + clinopyroxene +/- orthopyroxene with microlites of Ti-magnetite. Olivine (Fo(83-88)) is rare and believed to be dominantly antecrystic. An increase in the extent and frequency of reverse zoning in phenocrysts, sieve-textured plagioclase and the occurrence of antecrystic phases in post-caldera lavas record a shift to dynamic conditions, allowing the interaction of magma batches that were previously distinct. Pyroxene thermobarometry suggests crystallization at 950-1200 degrees C and 0 center dot 8-1 center dot 8 kbar. Volatile measurements of glassy melt inclusions indicate a maximum H2O content of 4 center dot 16 wt % H2O, and CO2-H2O saturation curves indicate that crystallization occurred at two levels, at depths of 4-5 center dot 5 km and 1 center dot 5-2 center dot 5 km. Major and trace element models suggest that the compositions of the majority of the samples represent a differentiation trend whereby the dacite was produced by 65% fractional crystallization of the most primitive basaltic andesite. Trace element models suggest that the sub-arc mantle source is the residuum of depleted Indian mid-ocean ridge basalt mantle (IDMM-1% melt), whereas radiogenic isotope data imply addition of 0 center dot 2% average Tongan sediment melt and a fluid component derived from the subducted altered Pacific oceanic crust. A horizontal array on the U-Th equiline diagram and Ra excesses of up to 500% suggest fluid addition to the mantle wedge within the last few thousand years. Time-integrated (Ra-226/Th-230) vs Sr/Th and Ba/Th fractionation models imply differentiation timescales of up to 4500 years for the dacitic magma compositions at Tofua.

One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Although the use of ball milling to induce reactions between solids (mechanochemical synthesis) can provide lower-waste routes to chemical products by avoiding solvent during the reaction, there are further potential advantages in using one-pot multistep syntheses to avoid the use of bulk solvents for the purification of intermediates. We report here two-step syntheses involving formation of salen-type ligands from diamines and hydroxyaldehydes followed directly by reactions with metal salts to provide the corresponding metal complexes. Five salen-type ligands 2,2'-[1,2-ethanediylbis[(E)-nitrilomethylidyne]] bisphenol, ` salenH2', 1; 2,2'-[(+/-)-1,2-cyclohexanediylbis-[(E)-nitrilomethylidyne]] bis-phenol, 2; 2,2'-[1,2-phenylenebis( nitrilomethylidyne)]-bis-phenol, ` salphenH2' 3; 2-[[(2-aminophenyl) imino] methyl]-phenol, 4; 2,2'-[(+/-)-1,2-cyclohexanediylbis[(E)-nitrilomethylidyne]]-bis[4,6-bis(1,1-dimethylethyl)]-phenol, ` Jacobsen ligand', 5) were found to form readily in a shaker-type ball mill at 0.5 to 3 g scale from their corresponding diamine and aldehyde precursors. Although in some cases both starting materials were liquids, ball milling was still necessary to drive those reactions to completion because precipitation of the product and or intermediates rapidly gave in thick pastes which could not be stirred conventionally. The only ligand which required the addition of solvent was the Jacobsen ligand 5 which required 1.75 mol equivalents of methanol to go to completion. Ligands 1-5 were thus obtained directly in 30-60 minutes in their hydrated forms, due to the presence of water by-product, as free-flowing yellow powders which could be dried by heating to give analytically pure products. The one-armed salphen ligand 4 could also be obtained selectively by changing the reaction stoichiometry to 1 : 1. SalenH(2) 1 was explored for the onepot two-step synthesis of metal complexes. In particular, after in situ formation of the ligand by ball milling, metal salts (ZnO, Ni(OAc)2 center dot 4H(2)O or Cu(OAc)(2)center dot H2O) were added directly to the jar and milling continued for a further 30 minutes. Small amounts of methanol (0.4-1.1 mol equivalents) were needed for these reactions to run to completion. The corresponding metal complexes [M(salen)] (M = Zn, 6; Ni, 7; or Cu, 8) were thus obtained quantitatively after 30 minutes in hydrated form, and could be heated briefly to give analytically pure dehydrated products. The all-at-once ` tandem' synthesis of [Zn(salen)] 6 was also explored by milling ZnO, ethylene diamine and salicylaldehyde together in the appropriate mole ratio for 60 minutes. This approach also gave the target complex selectively with no solvent needing to be added. Overall, these syntheses were found to be highly efficient in terms of time and the in avoidance of bulk solvent both during the reaction and for the isolation of intermediates. The work demonstrates the applicability of mechanochemical synthesis to one-pot multi-step strategies.

Mechanochemical interconversion between discrete complexes and coordination networks - formal hydration/dehydration by LAG

Using a small planetary ball mill, liquid-assisted grinding (LAG) of metal salts or oxides (ZnO, CdO, CdCO3, Cu(OAc)(2)center dot H2O, Co(OAc)(2)center dot 4H(2)O, Mn(OAc)(2)center dot 4H(2)O, Ni(OAc)(2)center dot 4H(2)O, FeSO4 center dot 7H(2)O) with two equivalents of isonicotinic acid (HINA) and small amounts of water ( up to 5.6 molar equivalents) gave discrete aquo complexes trans-[M(INA)(2)(OH2)(4)] (M = Zn, Cd, Cu, Fe, Co, Ni, Mn) efficiently within 30 min. For M = Zn, Cd and Cu these complexes readily undergo reversible formal dehydration to the extended network structures [M(INA)(2)] (M = Zn, Cu) or [Cd(INA)(2)(OH2)]center dot DMF by further LAG with non-aqueous liquids such as methanol or DMF. Overall, the mechanochemical dehydrations are more effective than heating or immersion in bulk solvents. The work demonstrates a two-step mechanochemical synthesis of coordination networks via discrete aquo complexes which may be preferable to single step reactions or grinding-annealing procedures in some cases. For example, the two step method was the only way to prepare [Cd(INA)(2)(OH2)]center dot DMF mechanochemically and the porous network Cu(INA)(2) could not be obtained from the aquo complex by heating.

Microelectrode Voltammetry of Dioxygen Reduction in a Phosphonium Cation-Based Room-Temperature Ionic Liquid: Quantitative Studies

Microelectrode voltammetry is used to study the electrochemical reduction of dioxygen, O-2, in the room-temperature ionic liquid trihexyl(tetradecyl)phosphonium trifluorotris(pentafluoroethyl)phosphate [P6,6,6,14][FAP]. The nature of the unusual voltammetric waves is quantitatively modeled via digital simulation with the aim of clarifying apparent inconsistencies in the literature. The reduction is shown to proceed via a two-electron reaction and involve the likely capture of a proton from the solvent system. The oxidative voltammetric signals seen at fast scan rates are interpreted as resulting from the reoxidation of HO2 center dot. In the presence of large amounts of dissolved carbon dioxide the reductive currents decrease by a factor of ca. two, consistent with the trapping of the superoxide radical, O-2(center dot), intermediate in the two-electron reduction process.

On the antioxidant properties of erythropoietin and its association with the oxidative-nitrosative stress response to hypoxia in humans

Aim: The aim of this study was to examine if erythropoietin (EPO) has the potential to act as a biological antioxidant and determine the underlying mechanisms.

Methods: The rate at which its recombinant form (rHuEPO) reacts with hydroxyl (HO center dot), 2,2-diphenyl-1-picrylhydrazyl (DPPH center dot) and peroxyl (ROO center dot) radicals was evaluated in-vitro. The relationship between the erythopoietic and oxidative-nitrosative stress response to poikilocapneic hypoxia was determined separately in-vivo by sampling arterial blood from eleven males in normoxia and following 12 h exposure to 13% oxygen. Electron paramagnetic resonance spectroscopy, ELISA and ozone-based chemiluminescence were employed for direct detection of ascorbate (A(center dot-)) and N-tert-butyl-a-phenylnitrone spin-trapped alkoxyl (PBN-OR) radicals, 3-nitrotyrosine (3-NT) and nitrite (NO2-).

Results: We found rHuEPO to be a potent scavenger of HO center dot (k(r) = 1.03-1.66 x 10(11) M-1 s(-1)) with the capacity to inhibit Fenton chemistry through catalytic iron chelation. Its ability to scavenge DPPH. and ROO center dot was also superior compared to other more conventional antioxidants. Hypoxia was associated with a rise in arterial EPO and free radical-mediated reduction in nitric oxide, indicative of oxidative-nitrosative stress. The latter was confirmed by an increased systemic formation of A(center dot-), PBN-OR, 3-NT and corresponding loss of NO2- (P <0.05 vs. normoxia). The erythropoietic and oxidative-nitrosative stress responses were consistently related (r =-0.52 to 0.68, P <0.05).

Conclusion: These findings demonstrate that EPO has the capacity to act as a biological antioxidant and provide a mechanistic basis for its reported cytoprotective benefits within the clinical setting.