N-methyl-N-alkylpyrrolidinium bis(perfluoroethylsulfonyl)amide ([NPf2]–) and tris(trifluoromethanesulfonyl)methide ([CTf3]–) salts : synthesis and characterization

Novel salts based the pyrrolidinium cation [C_nmpyr]⁺ (where n denote the number of carbons in the straight alkyl chain) and either the [NPf₂]^– or [CTf₃]^– anions have been synthesized and characterized to determine their thermal behaviour, stability, and conductivity. [C₁mpyr][NPf₂], [C₂mpyr][NPf₂], and [C₁mpyr][CTf₃] exhibit behaviour indicative of a plastic crystal phase. Both [C₃mpyr][NPf₂] and [C₄mpyr][NPf₂] are RTILs, while all of the [CTf₃]^– salts, have melting points above 60°C. [C₃mpyr][NPf₂] exhibited the widest electrochemical window of 5.5 V. The [NPf2]– salt exhibited similar reductive limits to the [NTf₂]^– anion, –3.2 V versus Fc⁺|Fc, while [CTf₃]^– had lower reductive stability. The [CTf₃]^– salts were more stable towards oxidation, +2.5 V versus Fc⁺|Fc, compared to the [NPf₂]^– and [NTf₂]^– salts.

Web-building spiders attract prey by storing decaying matter

The orb-weaving spider Nephila edulis incorporates into its web a band of decaying animal and plant matter. While earlier studies demonstrate that larger spiders utilise these debris bands as caches of food, the presence of plant matter suggests additional functions. When organic and plastic items were placed in the webs of N. edulis, some of the former but none of the latter were incorporated into the debris band. Using an Y-maze olfactometer, we show that sheep blowflies Lucilia cuprina are attracted to recently collected debris bands, but that this attraction does not persist over time. These data reveal an entirely novel foraging strategy, in which a sit-and-wait predator attracts insect prey by utilising the odours of decaying organic material. The spider's habit of replenishing the debris band may be necessary to maintain its efficacy for attracting prey.

Texture selection mechanisms in uniaxially extruded magnesium alloys

Extrusion textures in magnesium alloys are of high interest due to their influence on yield asymmetry. This data supports work describing three mechanisms of texture selection that may play a role during extrusion. These mechanisms involve localized differences in deformation at the grain level, the change in local environment experienced by grain boundary bulges and shear banding. The work employs visco-plastic crystal plasticity and electron backscattering diffraction.

Comportamento dos óxidos de ferro da fração argila e do fósforo adsorvido, em diferentes sistemas de colheita de cana-de-açúcar

In agriculture, the search for higher crop yields based on sustainable soil management has led to a gradual pursuit of knowledge of the variables related to production systems. The identification of the causes of variability of these properties has become a part of strategic planning in the sugar and ethanol industry. This study investigated the spatial variability of iron oxides in the clay fraction and its relationship to soil physical and chemical properties in different sugarcane cultivation systems in the region of Ribeirão Preto, São Paulo State. Two 1-ha plots were outlined in areas with mechanical and manual harvesting systems. Soil samples were taken at 126 points from the 0.00-0.25 m layer in both areas. The mineralogical and chemical data were subjected to geostatistical analyses, to determine the spatial dependence, semivariograms and kriging maps of the properties. To analyze the correlation between the parameters cross-semivariograms were constructed. The spatial variability of chemical properties was greater in areas with mechanical harvesting than burnt harvesting (manual harvesting), whereas the range of the mineralogical properties was largest in the area of green-harvested sugarcane. The properties organic matter, mean crystal diameter goethite had a negatively spatial correlation, while clay was positive correlated with P sorption in the two sugarcane harvest systems.

Polychlorinated biphenyls and organochlorine pesticides in plastics ingested by seabirds

The occurrence of plastic objects in the digestive tract was assessed in eight species of Procellariiformes collected in southern Brazil and the occurrence of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the ingested plastics pellets and plastic fragments was evaluated. PCBs were detected in plastic pellets (491 ng g(-1)) and plastic fragments (243-418 ng g(-1)). Among the OCPs, p,p`-DDE had the highest concentrations, ranging from 68.0 to 99.0 ng g(-1). The occurrence of organic pollutants in post-consumer plastics supports the fact that plastics are an important source carrying persistent organic pollutants in the marine environment. Although transfer through the food chain may be the main source of exposure to POPs to seabirds, plastics could be an additional source for the organisms which ingest them, like Procellariiformes which are the seabirds most affected by plastic pollution. (c) 2010 Elsevier Ltd. All rights reserved.

Physical properties, velocity and attenuation characteristics, and mineralogy of gabbros from ODP Hole 176-735B

Laboratory compressional wave (Vp) and shear wave (Vs) velocities were measured as a function of confining pressure for the gabbros from Hole 735B and compared to results from Leg 118. The upper 500 m of the hole has a Vp mean value of 6895 m/s measured at 200 MPa, and at 500 meters below seafloor (mbsf), Vp measurements show a mean value of 7036 m/s. Vs mean values in the same intervals are 3840 m/s and 3857 m/s, respectively. The mean Vp and Vs values obtained from log data in the upper 600 m are 6520 and 3518 m/s, respectively. These results show a general increase in velocity with depth and the velocity gradients estimate an upper mantle depth of 3.32 km. This value agrees with previous work based on dredged samples and inversion of rare element concentrations in basalts dredged from the conjugate site to the north of the Atlantis Bank. Laboratory measurements show Vp anisotropy ranging between 0.4% and 8.8%, with the majority of the samples having values less than 3.8%. Measurements of velocity anisotropy seem to be associated with zones of high crystal-plastic deformation with predominant preferred mineral orientations of plagioclase, amphiboles, and pyroxenes. These findings are consistent with results on gabbros from the Hess Deep area and suggest that plastic deformation may play an important role in the seismic properties of the lower oceanic crust. In contrast to ophiolite studies, many of the olivine gabbros show a small degree of anisotropy. Log derived Vs anisotropy shows an average of 5.8% for the upper 600 m of Hole 735B and tends to decrease with depth where the overburden pressure and the age of the crustal section suggests closure of cracks and infilling of fractures by alteration minerals. Overall the results indicate that the average shear wave splitting in Hole 735B might be influenced by preferred structural orientations and the average value of shear wave splitting may not be a maximum because structural dips are <90°. The maximum fast-wave orientation values could be influenced by structural features striking slightly oblique to this orientation or by near-field stress concentrations. However, flexural wave dispersion analyses have not been performed to confirm this hypothesis or to indicate to what extent the near-field stresses may be influencing shear wave propagation. Acoustic impedance contrasts calculated from laboratory and logging data were used to generate synthetic seismograms that aid in the interpretation of reflection profiles. Several prominent reflections produced by these calculations suggest that Fe-Ti oxides and shear zones may contribute to the reflective nature of the lower oceanic crust. Laboratory velocity attenuation (Q) measurements from below 500 m have a mean value of 35.1, which is consistent with previous vertical seismic profile (VSP) and laboratory measurements on the upper 500 m.

Enhancement of ‘dry’ proton conductivity by self-assembled nanochannels in all-solid polyelectrolytes

Proton transport has been recognized as an essential process in many biological systems, as well as electrochemical devices including fuel cells and redox flow batteries. In the present study, we address the pressing need for solvent-free proton conducting polymer electrolytes for high-temperature PEM fuel cell applications by developing a novel all-solid polyelectrolyte membrane with a self-assembled proton-channel structure. We show that this self-assembled nanostructure endows the material with exciting ‘dry’ proton conductivity at elevated temperatures, as high as 0.3 mS cm−1 at 120 °C, making it an attractive candidate for high-temperature PEM fuel cell applications. Based on the combined investigation of solid-state NMR, FTIR and conductivity measurements, we propose that both molecular design and nano-scale structures are essential for obtaining highly conductive anhydrous proton conductors.

Crystal structures of imidazolium bis(trifluoromethanesulfonyl)imide 'ionic liquid' salts: the first organic salt with a cis-TFSI anion conformation

Crystal structures of two examples of an important class of ionic liquids, 1,3-dimethylimidazolium and 1,2,3-triethylimidazolium bis(trifluoromethanesulfonyl)imide have been characterized by single crystal X-ray diffraction. The anion in the 1,3-dimethylimidazolium example (mp 22 degreesC), adopts an unusual cis-geometry constrained by bifurcated cation-anion C-H...O hydrogen-bonds from the imidazolium cation to the anion resulting in the formation of fluorous layers within the solid-state structure. In contrast, in the 1,2,3-triethylimidazolium salt (mp 57 degreesC), the ions are discretely packed with only weak C-H...O contacts between the ions close to the van der Waals separation distances, and with the anion adopting the twisted conformation observed for all other examples from the limited set of organic bis( trifluoromethanesulfonyl) imide crystal structures. The structures are discussed in terms of the favorable physical properties that bis(trifluoromethanesulfonyl) imide anions impart in ionic liquids.

Increasing ionic conductivity and mechanical strength of a plastic electrolyte by inclusion of a polymer

in this contribution we present a soft matter solid electrolyte which was obtained by inclusion of a polymer (polyacrylonitrile, PAN) in LiClO4/LiTFSI-succinonitrile (SN), a semi-solid organic plastic electrolyte. Addition of the polymer resulted in considerable enhancement in ionic conductivity as well as mechanical strength of LiX-SN (X=ClO4, TFSI) plastic electrolyte. Ionic conductivity of 92.5%-[1 M LiClO4-SN]:7.5%-PAN (PAN amount as per SN weight) composite at 25 degrees C recorded a remarkably high value of 7 x 10(-3) Omega(-1) cm(-1), higher by few tens of order in magnitude compared to 1 M LiClO4-SN. Composite conductivity at sub-ambient temperature is also quite high. At -20 degrees C, the ionic conductivity of (100 -x)%-[1 M LiClO4-SN]:x%-PAN composites are in the range 3 x 10(-5)-4.5 x 10(-4) Omega(-1) cm(-1), approximately one to two orders of magnitude higher with respect to 1 M LiClO4-SN electrolyte conductivity. Addition of PAN resulted in an increase of the Young's modulus (Y) from Y -> 0 for LiClO4-SN to a maximum of 0.4MPa for the composites. Microstructural studies based on X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy suggest that enhancement in composite ionic conductivity is a combined effect of decrease in crystallinity and enhanced trans conformer concentration. (c) 2008 Elsevier Ltd. All rights reserved.

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

Crystal Coulomb energies: I. Organic donor-acceptor complexes--a review. II. Classical Ewald calculations of the Coulomb binding energy of four donor-acceptor crystals and Wurster's blue perchlorate. III. A rapid-convergence quantum-mechanical formalism for crystal electronic energies

Chapter I

Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε₁ (per DA pair) gained in ionizing a DA lattice exceeds the cost 2ε_o of ionizing each DA pair, ε₁ + ε_o less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D⁺ and A^-). The magnetic properties of the DA crystals are discussed.

Chapter II

A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy E_C due to classical monopole-monopole interactions for crystals of any symmetry. The precision of E_C values obtained is high: the uncertainties, estimated by the effect on E_C of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in E_C due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.

E_C for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. E_C for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.

EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) E_C = -4.0 eV while 2ε_o = 4.6₅ eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) E_C = -4.4 eV, while 2ε_o = 5.0 eV: again EC falls short of 2ε₁. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) E_C = -4.5 eV, 2ε_o = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) E_C = -4.3 eV, 2ε_o = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.

Chapter III

A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]^XT, direct Coulomb [λλ/λ'λ']^XT and exchange Coulomb [λλ'/λ'λ]^XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]^XT, [λλ/λ'λ']^XT, and [λλ/λ'λ]^XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]^XT, [λλ/λ'λ']^XT and [λλ'/λ'λ]^XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]^XT, etc., where some of the portions contain the Gaussian factor.

Lead(II) chloride ionic liquids and organic/inorganic hybrid materials - a study of chloroplumbate(II) speciation

A range of chloroplumbate(II) organic salts, based on the two cations, 1-ethyl-3-methylimidazolium and trihexyl(tetradecyl) phosphonium, was prepared by ionothermal synthesis. Depending on the structure of the organic cation and on the molar ratio of PbCl2 in the product,.PbCl2, the salts were room-temperature ionic liquids or crystalline organic/inorganic hybrid materials. The solids were studied using Raman spectroscopy; the crystal structure of [C(2)mim]{PbCl3} was determined and shown to contain 1D infinite chloroplumbate(II) strands formed by edge-sharing tetragonal pyramids of pentacoordinate (PbCl5) units. The liquids were analysed using Pb-207 NMR and Raman spectroscopies, as well as viscometry. Phase diagrams were constructed based on differential scanning calorimetry (DSC) measurements. Discrete anions: [PbCl4](2-) and [PbCl3](-), were detected in the liquid state. The trichloroplumbate(II) anion was shown to have a flexible structure due to the presence of a stereochemically-active lone pair. The relationship between the liquid phase anionic speciation and the structure of the corresponding crystalline products of ionothermal syntheses was discussed, and the data were compared with analogous tin(II) systems.

Effect of Imidazolium-based Ionic Liquids on the nanoscale morphology of CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane) metal-organic semiconductors

We demonstrate for the first time the ionic-liquid-mediated synthesis of nanostructured CuTCNQ by the simple immersion of copper in a solution of TCNQ where the viscosity of the medium significantly impacts the corrosion–crystallization process and the final morphology of the material.

Study of Ion Transport in Lithium Perchlorate-Succinonitrile Plastic Crystalline Electrolyte via Ionic Conductivity and in Situ Cryo-Crystallography

Ion transport mechanism in lithium perchlorate (LiClO4)-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0-1 M LiClO4-SN samples. Activation energy due to solvent configurational changes, that is, trans-gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO4-SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.

Ionic Liquids and Microwaves in Promotion of Organic Synthesis : Friedel-Crafts reaction, deuterolabelling and O-Demethylation

The use of ionic liquids in chemical research has gained considerable interest and activity in recent years. Due to their unique and varied physicochemical properties, in comparison to molecular solvents, the potential applications for ionic liquids are enormous. The use of microwave irradiation, as a powerful dielectric heating technique, in synthetic organic chemistry has been known since 1986. Since then, it has gained significant recognition for its research and application in both academia and industry. The use of either ionic liquids or microwave irradiation in synthetic organic chemistry has been known to afford improved, alternative or complimentary selectivities, in comparison to traditional processes. In this study, the use of ionic liquids as solvents, co-solvents and catalytic media was explored in Friedel-Crafts, deuterolabelling and O-demethylation reactions. Alternative methods for the production of a variety of aromatic ketones using the Friedel-Crafts acylation methodology were investigated using ionic liquid catalyst or ionic liquid acidic additive systems. The disclosed methods, i.e. metal bistriflamides and chloroindate ionic liquids systems, possessed good catalytic activity in the synthesis of typical benzophenones. These catalytic systems were also recyclable. Microwave irradiation was found to be useful in the synthesis of various polyhydroxydeoxybenzoins and arylpropanones as synthetic precursors to naturally occurring or potentially bioactive compounds. Under optimized condition, the reaction occurred in only four minutes using systems such as [bmim][NTf2]/HNTf2 and [bmim][BF4]/BF3·OEt2. Naturally occurring polyphenols, such as isoflavones, can possess various types of biological or pharmacological activity. In particular, some are noted for their beneficial effects on human health. Isotopically labelled analogues of polyphenols are valuable as analytical standards in the quantification of these compounds from biological matrices. A new strategy for deuterolabelling of polyphenols was developed using ionic liquids as co-solvents and 35% DCl/D2O, as a cheap deuterium source, under microwave irradiation. Under these conditions, perdeuterated compounds were achieved in short reaction times, in high isotopic purity and in excellent yields. An O-demethylation reaction was developed, using an ionic liquid reaction medium with BBr3 for the deprotection of a variety methyl protected polyphenolic compounds, such as isoflavons and lignans. This deprotection procedure was found to be very practical as the reaction occurred under mild reaction conditions and in short reaction times. The isolation and purification steps were particularly straightforward and high yielding, in comparison to traditional methods.