Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg−1 and 362 mgCu kg−1) and Pb/Zn mine (4550 mgPb kg−1 and 908 mgZn kg−1) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element.

Penciclovir solubility in Eudragit films: a comparison of X-ray, thermal, microscopic and release rate techniques

The solubility of penciclovir (C10N5O3H17) in a novel film formulation designed for the treatment of cold sores was determined using X-ray, thermal, microscopic and release rate techniques. Solubilities of 0.15–0.23, 0.44, 0.53 and 0.42% (w/w) resulted for each procedure. Linear calibration lines were achieved for experimentally and theoretically determined differential scanning calorimetry (DSC) and X-ray powder diffractometry (XRPD) data. Intra- and inter-batch data precision values were determined; intra values were more precise. Microscopy was additionally useful for examining crystal shape, size distribution and homogeneity of drug distribution within the film. Whereas DSC also determined melting point, XRPD identified polymorphs and release data provided relevant kinetics.

Bile salt composition is secondary to bile salt concentration in determining hydrocortisone and progesterone solubility in intestinal mimetic fluids.

Simulated intestinal fluids (SIFs) used to assay the solubility of orally administered drugs are typically based on a single bile salt; sodium taurocholate (STC). The aim of this study was to develop mimetic intestinal fluids with a closer similarity to physiological fluids than those reported to date by developing a mixed bile salt (MBS) system (STC, sodium glycodeoxycholate, sodium deoxycholate; 60:39:1) with different concentrations of lecithin, the preponderant intestinal phospholipid. Hydrocortisone and progesterone were used as model drugs to evaluate systematically the influence of SIF composition on solubility. Increasing total bile salt concentration from 0 to 30 mM increased hydrocortisone and progesterone solubility by 2- and ∼25-fold, respectively. Accordingly, higher solubilities were measured in the fed-state compared to the fasted-state SIFs. Progesterone showed the greatest increases in solubility in STC and MBS systems (2-7-fold) compared to hydrocortisone (no significant change; P>0.05) as lecithin concentration was increased. Overall, MBS systems gave similar solubility profiles to STC. In conclusion, the addenda of MBS and lecithin were found to be secondary to the influence of BS concentration. These data provide a foundation for the design of more bio-similar media for pivotal decision-guiding assays in drug development and quality control settings.

Exploring the Factors Affecting the Solubility of Chitosan in Water

We explore the role of crystallinity and inter- or intramolecular forces in chitosan for its solubility in water and demonstrate the expansion of its solubility to a wider pH range. Due to its semicrystalline nature, derived mainly from inter- and intramolecular hydrogen bonds, chitosan is water-soluble only at pH < 6. In acidic conditions, its amino groups can be partially protonated resulting in repulsion between positively charged macrochains, thereby allowing diffusion of water molecules and subsequent solvation of macromolecules. We show that chemical disruption of chitosan crystallinity by partial re-acetylation or physical disruption caused by the addition of urea and guanidine hydrochloride broadens the pH-solubility range for this biopolymer.

Low-molecular-weight gelators: Elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model

This paper highlights the key role played by solubility in influencing gelation and demonstrates that many facets of the gelation process depend on this vital parameter. In particular, we relate thermal stability (T-gel) and minimum gelation concentration (MGC) values of small-molecule gelation in terms of the solubility and cooperative self-assembly of gelator building blocks. By employing a van't Hoff analysis of solubility data, determined from simple NMR measurements, we are able to generate T-calc values that reflect the calculated temperature for complete solubilization of the networked gelator. The concentration dependence of T-calc allows the previously difficult to rationalize "plateau-region" thermal stability values to be elucidated in terms of gelator molecular design. This is demonstrated for a family of four gelators with lysine units attached to each end of an aliphatic diamine, with different peripheral groups (Z or Bee) in different locations on the periphery of the molecule. By tuning the peripheral protecting groups of the gelators, the solubility of the system is modified, which in turn controls the saturation point of the system and hence controls the concentration at which network formation takes place. We report that the critical concentration (C-crit) of gelator incorporated into the solid-phase sample-spanning network within the gel is invariant of gelator structural design. However, because some systems have higher solubilities, they are less effective gelators and require the application of higher total concentrations to achieve gelation, hence shedding light on the role of the MGC parameter in gelation. Furthermore, gelator structural design also modulates the level of cooperative self-assembly through solubility effects, as determined by applying a cooperative binding model to NMR data. Finally, the effect of gelator chemical design on the spatial organization of the networked gelator was probed by small-angle neutron and X-ray scattering (SANS/SAXS) on the native gel, and a tentative self-assembly model was proposed.

Strongly nucleophilic RhI centre in square-planar complexes with terdentate (κ3) 2,2′:6′,2′′-terpyridine ligands: crystallographic, electrochemical and density functional theoretical studies

Rh-I-terpyridine complexes have been unambiguously formed for the first time. The 2,21:6',2"-terpyridine (tpy), 4'-chloro-2,2':6',2"-terpyridine (4'-Cl-tpy) and 4'-(tert-butyldimethylsilyl-ortho-carboranyl)-2,2':6',2"-terpyridine (carboranyl-tpy) ligands were used for successful syntheses and characterisation of the corresponding Rh-I complexes with halide coligands, [Rh(X)(4'-Y-terpyridine)] (X = Cl, Y = H, Cl, carboranyl; X = Br, Y = H). All four neutral Rh-tpy complexes are square planar, with Rh-X bonds in the plane of the 4'-Y-terpyridine ligands. Full characterisation of these dark blue, highly air-sensitive compounds was hampered by their poor solubility in various organic solvents. This is mainly due to the formation of pi-stacked aggregates, as evidenced by the crystal structure of [Rh(Cl)(tpy)]; in addition, [Rh(Cl)(carboranyl-tpy)] merely forms discrete dimers. The (bonding) properties of the novel Rh-I-terpyridine complexes have been studied with single-crystal X-ray diffraction, (time-dependent) density functional theoretical (DFT) calculations, far-infrared spectroscopy, electronic absorption spectroscopy and cyclic voltammetry. From DFT calculations, the HOMO of the studied Rh-I-terpyridine complexes involves predominantly the metal centre, while the LUMO resides on the terpyridine ligand. Absorption bands of the studied complexes in the visible region (400-900 nm) can be assigned to MLCT and MLCT/XLCT transitions. The relatively low oxidation potentials of [Rh(X)(tpy)] (X = Cl, Br) point to a high electron density on the metal centre. This makes the Rh-I-terpyridine complexes strongly nucleophilic and (potentially) highly reactive towards various (small) substrate molecules containing carbon-halide bonds.

Return of the 'Angry Woman': authenticating female physical action in contemporary cinema

In 1999, Elizabeth Hills pointed up the challenges that physically active women on film still posed, in cultural terms, and in relation to certain branches of feminist theory . Since then, a remarkable number of emphatically active female heroes have appeared on screen, from 'Charlie’s Angels' to 'Resident Evil', 'Aeon Flux', and the 'Matrix' and 'X-Men' trilogies. Nevertheless, in a contemporary Western culture frequently characterised as postfeminist, these seem to be the ‘acceptable face’ – and body – of female empowerment: predominantly white, heterosexual, often scantily clad, with the traditional hero’s toughness and resolve re-imagined in terms of gender-biased notions of decorum: grace and dignity alongside perfect hair and make-up, and a body that does not display unsightly markers of physical exertion. The homogeneity of these representations is worth investigating in relation to critical claims that valorise such air-brushed, high-kicking 'action babes' for their combination of sexiness and strength, and the feminist and postfeminist discourses that are refracted through such readings. Indeed, this arguably ‘safe’ set of depictions, dovetailing so neatly with certain postfeminist notions of ‘having it all’, suppresses particular kinds of spectacles in relation to the active female body: images of physical stress and extension, biological consequences of violence and dangerous motivations are all absent. I argue that the untidy female exertions refused in popular “action babe” representations are now erupting into view in a number of other contemporaneous movies – 'Kill Bill' Vols 1 & 2, 'Monster', and 'Hard Candy' – that mark the return of that which is repressed in the mainstream vision of female power – that is, a more viscerally realistic physicality, rage and aggression. As such, these films engage directly with the issue of how to represent violent female agency. This chapter explores what is at stake at a representational level and in terms of spectatorial processes of identification in the return of this particularly visceral rendering of the female avenger.

Constraining a North Atlantic Ocean general circulation model with chlorofluorocarbon observations

Measurements of anthropogenic tracers such as chlorofluorocarbons and tritium must be quantitatively combined with ocean general circulation models as a component of systematic model development. The authors have developed and tested an inverse method, using a Green's function, to constrain general circulation models with transient tracer data. Using this method chlorofluorocarbon-11 and -12 (CFC-11 and -12) observations are combined with a North Atlantic configuration of the Miami Isopycnic Coordinate Ocean Model with 4/3 degrees resolution. Systematic differences can be seen between the observed CFC concentrations and prior CFC fields simulated by the model. These differences are reduced by the inversion, which determines the optimal gas transfer across the air-sea interface, accounting for uncertainties in the tracer observations. After including the effects of unresolved variability in the CFC fields, the model is found to be inconsistent with the observations because the model/data misfit slightly exceeds the error estimates. By excluding observations in waters ventilated north of the Greenland-Scotland ridge (sigma (0) < 27.82 kg m(-3); shallower than about 2000 m), the fit is improved, indicating that the Nordic overflows are poorly represented in the model. Some systematic differences in the model/data residuals remain and are related, in part, to excessively deep model ventilation near Rockall and deficient ventilation in the main thermocline of the eastern subtropical gyre. Nevertheless, there do not appear to be gross errors in the basin-scale model circulation. Analysis of the CFC inventory using the constrained model suggests that the North Atlantic Ocean shallower than about 2000 m was near 20% saturated in the mid-1990s. Overall, this basin is a sink to 22% of the total atmosphere-to-ocean CFC-11 flux-twice the global average value. The average water mass formation rates over the CFC transient are 7.0 and 6.0 Sv (Sv = 10(6) m(3) s(-1)) for subtropical mode water and subpolar mode water, respectively.

Alternative syntheses of linear polyurethanes using masked isocyanate monomers

A range of linear polyurethanes featuring aliphatic, aromatic and ether residues have been prepared by co-polymerisation of novel 'masked' isocyanate A(2)-type monomers and diols. The reactive isocyanate monomers were generated in situ via the triphenylphosphine mediated decomposition of the heterocyclic disulfide, 1,2,4-dithiazolidine-3,5-dione. Two different synthetic approaches were examined and assessed for the construction of the novel A(2)-type monomers, which involved either coupling two 1,2,4-dithiazolidine-3,5-diones together through a spacer group or construction of 1,2,4-dithiazolidine-3,5-diones directly from diamines. The resulting polyurethanes were purified via solvent extraction and analysed using GPC, NMR and IR spectroscopic analyses. Molecular weight data were obtained and compared from both GPC and H-1 NMR (via end-group analysis) spectroscopic analysis. The thermal properties of the polyurethanes were determined using DSC and their solubility in common aprotic organic solvents was also assessed and related to their structural composition. (c) 2006 Elsevier B.V. All rights reserved.

Poly(ethylene glycol)-supported nitroxyls: branched catalysts for the selective oxidation of alcohols

Nitroxyl radicals such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) are highly selective oxidation catalysts for the conversion of primary alcohols into the corresponding aldehydes. In this study, direct tethering of TEMPO units onto linear poly(ethylene glycol) (PEG) has afforded macromolecular catalysts that exhibit solubility in both aqueous and organic solvents. Recovery of the dissolved polymer-supported catalyst has been carried out by precipitation with a suitable solvent such as diethyl ether. The high catalyst activities and selectivities associated traditionally with nitroxyl-mediated oxidations of alcohols are retained by the series of "linker-less" linear PEG-TEMPO catalysts in which the TEMPO moiety is coupled directly to the PEG support. Although the selectivity remains unaltered, upon recycling of the linker-less polymer-supported catalysts, extended reaction times are required to maintain high yields of the desired carbonyl compounds. Alternatively, attachment of two nitroxyl radicals onto each functionalized PEG chain terminus via a 5-hydroxyisophthalic acid linker affords branched polymer-supported catalysts. In stark contrast to the linker-less catalysts, these branched nitroxyls exhibit catalytic activities up to five times greater than 4-methoxy-TEMPO alone under similar conditions. In addition, minimal decrease in catalytic activity is observed upon recycling of these branched macromolecular catalysts via solvent-induced precipitation. The high catalytic activities and preservation of activity upon recycling of these branched systems is attributed to enhanced regeneration of the nitroxyl species as a result of intramolecular syn-proportionation.

endo-Selective (3+2) cycloaddition polymerizations of nitrone monomers with olefins utilising high pressure conditions

A high pressure mediated (3+2) cycloaddition polymerization strategy has been employed to afford linear poly(isoxazolidine) architectures. Under these high pressure conditions this cycloaddition process was found to afford primarily endoheterocycles which when translated to the polymerization should ultimately affect the tacticity and resultant properties of the polymer. The stereoselectivity occurred as a result of a lower volume of activation for the endo-transition state and the application of a 'type-I' regime (HOMODipole-LUMODipolarophile) cycloaddition process that features secondary orbital interactions within the extended molecular orbitals. A variety of linker segments were employed in an attempt to affect the physical properties of the polymeric cycloadducts such as T-g and solubility in order to tailor these materials for use in coating applications. (C) 2007 Elsevier Ltd. All rights reserved.

Production of pH-responsive microparticles by spray drying: investigation of experimental parameter effects on morphological and release properties

During spray drying, emphasis is placed on process optimisation to generate favourable particle morphological and flow properties. The effect of the initial feed solution composition on the drug release from the prepared microparticles is rarely considered. We investigated the effects of solvent composition, feed solution concentration and drug-loading on sodium salicylate, hydrocortisone and triamcinolone release from spray dried Eudragit L100 microparticles. Eudragit L100 is a pH-responsive polymer whose dissolution threshold is pH 6 so dissolution testing of the prepared microparticles at pH 5 and 1.2 illustrated non-polymer controlled burst release. Increasing the water content of the initial ethanolic feed solution significantly reduced hydrocortisone burst release at pH 5, as did reducing the feed solution concentration. These findings caution that changes in feed solution concentration or solvent composition not only affect particles’ morphological characteristics but can also negatively alter their drug release properties. This work also illustrate that drug-free microparticles can have different morphological properties to drug-loaded microparticles. Therefore, process optimisation needs to be carried out using drug-loaded systems. Depending on the physicochemical properties of the encapsulated API, drug-loading can affect the polymer solubility in the initial feed solution with consequent impact on microparticles morphological and release properties.