Visible light sensitisation of europium(III) luminescence in a 9-hydroxyphenal-1-one complex

The 9-hydroxyphenal-1-one ligand forms stable 3 : 1 complexes with trivalent lanthanides, in which it acts as an antenna suitable for the visible light excitation ( up to 475 nm) of the trivalent europium ion.

Identical extraction behavior and coordination of trivalent or hexavalent f-element cations using ionic liquid and molecular solvents

The extraction of both UO22+ and trivalent lanthanide and actinide ions (Am3+, Nd3+, Eu3+) by dialkylphosphoric or dialkylphosphinic acids from aqueous solutions into the ionic liquid, 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide has been studied and compared to extractions into dodecane. Radiotracer partitioning measurements show comparable patterns of distribution ratios for both the ionic liquid/aqueous and dodecane/aqueous systems, and the limiting slopes at low acidity indicate the partitioning of neutral complexes in both solvent systems. The metal ion coordination environment, elucidated from EXAFS and UV-visible spectroscopy measurements, is equivalent in the ionic liquid and dodecane solutions with coordination of the uranyl cation by two hydrogen-bonded extractant dimers, and of the trivalent cations by three extractant dimers. This is the first definitive report of a system where both the biphasic extraction equilibria and metal coordination environment are the same in an ionic liquid and a molecular organic solvent.

Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

Lanthanide(III) nitrobenzenesulfonates as new nitration catalysts: The role of the metal and of the counterion in the catalytic efficiency

Lanthanide(III) complexes of p-nitrobenzenesulfonic acid, Ln(p-NBSA)(3), m-nitrobenzenesulfonic acid, Ln(m-NBSA)(3), and 2,4-nitrobenzenesulfonic acid, Ln(2,4-NBSA)(3), were prepared, characterized and examined as catalyst for the nitration of benzene, toluene, xylenes, naphthalene, bromobenzene and chlorobenzene. The initial screening of the catalysts showed that lanthanum(III) complexes were more effective than the corresponding ytterbium(III) complexes, and that catalysts containing the bulky 2,4-NBSA ligand were less effective than the catalyst containing p-NBSA (nosylate) or m-NBSA ligands. Examination of a series of Ln(p-NBSA)(3) and Ln(m-NBSA)(3) catalysts revealed that there is a clear correlation between the ionic radii of the lanthanide(III) ions and the yields of nitration, with the lighter lanthanides being more effective. The X-ray single crystal structure of Yb(m-NBSA)(3).6H(2)O shows that two m-NBSA ligands are directly bound to the metal centre while the third ligand is not located in the first coordination sphere, but it is hydrogen bonded to one of the water molecules which is coordinated to ytterbium(III). NMR studies suggest that this structure is preserved under the conditions used in the nitration reaction. The structure of Yb(m-NBSA)(3) is markedly different from the structure of the well-known ytterbium(III) triflate catalyst. The coordination of the nitrobenzenesulfonate counterion to the lanthanide(III) ion suggests that steric effects might play an important role in determining the efficiency of these novel nitration catalysts. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Simultaneous biosorption of methylene blue and trivalent chromium onto olive stone

In this work, olive stone (OS) was utilized to investigate its capacity as biosorbent for methylene blue (MB) and Cr(III), which are usually present in textile industry effluents. Equilibrium and kinetic experiments were performed in batch experiments. The biosorption process followed pseudo-second-order kinetics. The equilibrium data were fitted with several models, but Langmuir and Sips models best reproduced the experimental results. Maximum biosorption capacities were 3.296 mg/g (0.0116 mmol/g) and 4.990 mg/g (0.0960 mmol/g) for MB and Cr(III), respectively. Several operation variables, such as
biosorbent mass, flow rate, and initial concentration on the removal of dye and metal, were evaluated in column system. The removal efficiency improved as OS mass increased and decreased when flow rate and initial concentration increased. Also, MB uptake was substantially decreased by increasing the initial concentration of Cr(III), ranging from 6.09 to 2.75 mg/g. These results show that the presence of Cr(III) significantly modifies the biosorption capacity of MB by the OS. These results suggest that OS is a potential low-cost food industry waste for textile industry wastewater treatment.

WHIRLBOB, the Whirlpool Based Variant of STRIBOB: Lighter, Faster, and Constant Time

WHIRLBOB, also known as STRIBOBr2, is an AEAD (Authenticated Encryption with Associated Data) algorithm derived from STRIBOBr1 and the Whirlpool hash algorithm. WHIRLBOB/STRIBOBr2 is a second round candidate in the CAESAR competition. As with STRIBOBr1, the reduced-size Sponge design has a strong provable security link with a standardized hash algorithm. The new design utilizes only the LPS or ρ component of Whirlpool in flexibly domain-separated BLNK Sponge mode. The number of rounds is increased from 10 to 12 as a countermeasure against Rebound Distinguishing attacks. The 8 ×8 - bit S-Box used by Whirlpool and WHIRLBOB is constructed from 4 ×4 - bit “MiniBoxes”. We report on fast constant-time Intel SSSE3 and ARM NEON SIMD WHIRLBOB implementations that keep full miniboxes in registers and access them via SIMD shuffles. This is an efficient countermeasure against AES-style cache timing side-channel attacks. Another main advantage of WHIRLBOB over STRIBOBr1 (and most other AEADs) is its greatly reduced implementation footprint on lightweight platforms. On many lower-end microcontrollers the total software footprint of π+BLNK = WHIRLBOB AEAD is less than half a kilobyte. We also report an FPGA implementation that requires 4,946 logic units for a single round of WHIRLBOB, which compares favorably to 7,972 required for Keccak / Keyak on the same target platform. The relatively small S-Box gate count also enables efficient 64-bit bitsliced straight-line implementations. We finally present some discussion and analysis on the relationships between WHIRLBOB, Whirlpool, the Russian GOST Streebog hash, and the recent draft Russian Encryption Standard Kuznyechik.

How fragmented was the British Holocene wildwood? Perspectives on the “Vera” grazing debate from the fossil beetle record

The reconstruction and structure of the European Holocene “wildwood” has been the focus of considerable academic debate. The ability of palaeoecological data and particularly pollen analysis to accurately reflect the density of wildwood canopy has also been widely discussed. Fossil insects, as a proxy for vegetation and landscape structure, provide a potential approach to address this argument. Here, we present a review and re-analysis of 36 early and mid-Holocene (9500-2000 cal BC) sub-fossil beetle assemblages from Britain, examining percentage values of tree, open ground and dung beetles as well as tree host data to gain an insight into vegetation structure, the role of grazing animals in driving such structure and establish independently the importance of different types of trees and associated shading in the early Holocene “wildwood”. Open indicator beetle species are persistently present over the entire review period, although they fluctuate in importance. During the early Holocene (9500-6000 cal BC), these indicators are initially high, at levels which are not dissimilar to modern data from pasture woodland. However, during the latter stages of this and the next period, 6000-4000 cal BC, open ground and pasture indicators decline and are generally low compared with previously. Alongside this pattern, we see woodland indicators generally increase in importance, although there are significant local fluctuations. Levels of dung beetles are mostly low over these periods, with some exceptions to this pattern, especially towards the end of the Mesolithic and in floodplain areas. Host data associated with the fossil beetles indicate that trees associated with lighter canopy conditions such as oak, pine, hazel and birch are indeed important components of the tree canopy during the earlier Holocene (c. 9500-6000 cal BC), in accordance with much of the current pollen literature. Beetles associated with more shade-tolerant trees (such as lime and elm) become more frequent in the middle Holocene (6000-4000 cal BC) suggesting that at this stage the woodland canopy was less open than previously, although open ground and pasture areas appear to have persisted in some locations. The onset of agriculture (4000-2000 cal BC) coincides with significant fluctuations in woodland composition and taxa. This is presumably as a result of human impact, although here there are significant regional variations. There are also increases in the amounts of open ground represented and especially in the levels of dung beetles present in faunas, suggesting there is a direct relationship between the activities of grazing animals and the development of more open areas. One of the most striking aspects of this review is the variable nature of the landscape suggested by the palaeoecological data, particularly but not exclusively with the onset of agriculture: some earlier sites indicate high variability between levels of tree-associated species on the one hand and the open ground beetle fauna on the other, indicating that in some locations, open areas were of local significance and can be regarded as important features of the Holocene landscape. The role of grazing animals in creating these areas of openness was apparently minimal until the onset of the Neolithic.

Near-infrared photoluminescence of lanthanide complexes containing the hemicyanine chromophore

The near-infrared luminescence properties of three (E)-N-hexadecyl-N',N'-dimethylamino-stilbazolium tetrakis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolonato) lanthanide(III) complexes are described. These three complexes, containing trivalent neodymium, erbium and ytterbium, respectively, show near-infrared luminescence in acetonitrile solution upon UV irradiation. Luminescence decay times have been measured. The complexes consist of a positively charged hemicyanine chromophore with a long alkyl chain and a tetrakis(pyrazolonato) lanthanide(III) anion. Because of the absence of an alpha-hydrogen atom in the pyrazolonato ligands, and because of the saturation of the coordination sphere by four bidentate ligands, the luminescence properties are enhanced when compared to, e.g. quinolinate complexes. (C) 2007 Elsevier Ltd. All rights reserved.

Visible-light-sensitized near-infrared luminescence from rare-earth complexes of the 9-hydroxyphenalen-1-one ligand

The unique absorption properties of the 9-hydroxyphenalen-1-one (HPHN) ligand have been exploited to obtain visible-light-sensitizable rare-earth complexes in 1: 3 and 1: 4 metal-to-ligand ratios. In both stoichiometries (1:3,tris,Ln(PHN)3;1:4, tetrakis, A[ Ln( PHN)(4)], with Ln being a trivalent rare-earth ion and A being a monovalent cation), the complexes of Nd(III),Er( III), and Yb(III) show typical near-infrared luminescence upon excitation with visible light with wavelengths up to 475 nm. The X-ray crystal structures of the tris complexes show solvent coordination to the central rare-earth ion, whereas in the tetrakis complexes, the four PHN-ligands form a protective shield around the central ion, preventing small solvent molecules from coordinating to the rare-earth ion, at least in the solid state.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

SHELL COLOUR IN CALLIOSTOMA ZIZYPHINUM (L.) FROM STRANGFORD LOUGH, N. IRELAND

Shells of Calliostoma zizyphinum taken from Strangford Lough, N. Ireland are divisible into three distinct colour forms: white (=var lyonsi) intermediate (a pale variegated form) and purple (a dark variegated form). The predominance of white and pale shelled individuals within and the absence of white Calliostoma outside the lough was confirmed. The proportions of animals with white and variegated shells at selected sites were almost identical with those previously documented, suggesting a temporal stability of colour form ratios. No differences in shell thickness and pedal adhesion were demonstrated between these forms. Snails with white shells reflect radiant heat better, have lighter coloured feet, move more rapidly, show a greater incidence of shell repair and are more frequently exposed on weed at low tide, than those with either intermediate or purple shells. Increased proportions of white individuals may be associated with high population densities. Under such circumstances, it is suggested that increased mobility may, by increasing dispersion, reduce intraspecific competition. In the event of exposure at low tide a white shell would help minimize thermal stress.

Biosorption of toxic chromium from aqueous phase by lignin: mechanism, effect of other metal ions and salts

Surface reaction methodology was implicated in the optimization of hexavalent chromium removal onto lignin with respect to the process parameters. The influence of altering the conditions for removal of chromium(VI), for instance; solution pH, ionic strength, initial concentration, the dose of biosorbent, presence of other metals (Zn and Cu), presence of salts and biosorption-desorption studies, were investigated. It was found that the biosorption capacity of lignin depends on solution pH, with a maximum biosorption capacity for chromium at pH 2. Experimental equilibrium data were fitted to five different isotherm models by non-linear regression method, however, the biosorption equilibrium data were well interpreted by the Freundlich isotherm. The maximum biosorption capacities (q(max)) obtained using Dubinin-Radushkevich and Khan isotherms for Cr(VI) biosorption are 31.6 and 29.1 mg/g. respectively. Biosorption showed pseudo second order rate kinetics at different initial concentrations of Cr(VI). The intraparticle diffusion study indicated that film diffusion may be involved in the current study. The percentage removal of chromium on lignin decreased significantly in the presence of NaHCO3 and K2P2O7 salts. Desorption data revealed that nearly 70% of the Cr(VI) adsorbed on lignin could be desorbed using 0.1 M NaOH. It was evident that the biosorption mechanism involves the attraction of both hexavalent chromium (anionic) and trivalent chromium (cationic) onto the surface of lignin. (C) 2011 Elsevier B.V. All rights reserved.