Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

Formation of vesicles through solvent assisted self-assembly of hydrophobic pentapeptides: encapsulation and pH responsive release of dyes by the vesicles

In the biomimetic design two hydrophobic pentapetides Boc-Ile-Aib-Leu-Phe-Ala-OMe ( I) and Boc-Gly-Ile-Aib-Leu-Phe-OMe (II) (Aib: alpha-aminoisobutyric acid) containing one Aib each are found to undergo solvent assisted self-assembly in methanol/water to form vesicular structures, which can be disrupted by simple addition of acid. The nanovesicles are found to encapsulate dye molecules that can be released by the addition of acid as confirmed by fluorescence microscopy and UV studies. The influence of solvent polarity on the morphology of the materials generated from the peptides has been examined systematically, and shows that fibrillar structures are formed in less polar chloroform/petroleum ether mixture and vesicular structures are formed in more polar methanol/water. Single crystal X-ray diffraction studies reveal that while beta-sheet mediated self-assembly leads to the formation of fibrillar structures, the solvated beta-sheet structure leads to the formation of vesicular structures. The results demonstrate that even hydrophobic peptides can generate vesicular structures from polar solvent which may be employed in model studies of complex biological phenomena.

Environmental oestrogens and breast cancer: long-term low-dose effects of mixtures of various chemical combinations

The incidence of breast cancer has risen worldwide to unprecedented levels in recent decades, making it now the major cancer of women in many parts of the world.1 Although diet, alcohol, radiation and inherited loss of BRCA1/2 genes have all been associated with increased incidence, the main identified risk factors are life exposure to hormones including physiological variations associated with puberty/pregnancy/menopause,1 personal choice of use of hormonal contraceptives2 and/or hormone replacement therapy.3–6 On this basis, exposure of the human breast to the many environmental pollutant chemicals capable of mimicking or interfering with oestrogen action7 should also be of concern.8 Hundreds of such environmental chemicals have now been measured in human breast tissue from a range of dietary and domestic exposure sources7 ,9 including persistent organochlorine pollutants (POPs),10 polybrominated diphenylethers and polybromobiphenyls,11 polychlorinated biphenyls,12 dioxins,13 alkyl phenols,14 bisphenol-A and chlorinated derivatives,15 as well as other less lipophilic compounds such as parabens (alkyl esters of p-hydroxybenzoic acid),16 but studies investigating any association between raised levels of such compounds and the development of breast cancer remain inconclusive.7–16 However, the functionality of these chemicals has continued to be assessed on the basis of individual chemicals rather than the environmental reality of long-term low-dose exposure to complex mixtures. This misses the potential for individuals to have high concentrations of different compounds but with a common mechanism of action. It also misses the complex interactions between chemicals and physiological hormones which together may act to alter the internal homeostasis of the oestrogenic environment of mammary tissue.

Displacement of methane by coadsorbed carbon dioxide is facilitated in narrow carbon nanopores

By using simulation methods, we studied the adsorption of binary CO2-CH4 mixtures on various CH4 preadsorbed carbonaceous materials (e.g., triply periodic carbon minimal surfaces, slit-shaped carbon micropores, and Harris's virtual porous carbons) at 293 K. Regardless of the different micropore geometry, two-stage mechanism of CH4 displacement from carbon nanospaces by coadsorbed CO2 has been proposed. In the first stage, the coadsorbed CO2 molecules induced the enhancement of CH4 adsorbed amount. In the second stage, the stronger affinity of CO2 to flat/curved graphitic surfaces as well as CO2-CO2 interactions cause the displacement of CH4 molecules from carbonaceous materials. The operating conditions of CO2-induced cleaning of the adsorbed phase from CH4 mixture component strongly depend on the size of the carbon micropores, but, in general, the enhanced adsorption field in narrow carbon ultramicropores facilitates the nonreactive displacement of CH4 by coadsorbed CO2. This is because in narrow carbon ultramicropores the equilibrium CO2/CH4 selectivity (i.e., preferential adsorption toward CO2) increased significantly. The adsorption field in wider micropores (i.e., the overall surface energy) for both CO2 and CH4 is very similar, which decreases the preferential CO2 adsorption. This suppresses the displacement of CH4 by coadsorbed CO2 and assists further adsorption of CH4 from the bulk mixture (i.e., CO2/CH4 mixing in adsorbed phase).

Lightly branched comb polyesters: application in fast drying solvent-borne coating formulations

Novel oxazoline-based comb-polymers possessing linoleyl or oleic side chains have been synthesized and used to produce low viscosity coatings. Inclusion of the polymers in model paint formulations results in coatings that exhibit faster drying times than commercially available alkyd resin formulations. The comb polymers were produced from diol substituted oxazoline monomers that were synthesized through a scalable, solvent free protocol and purified by simple recrystallisation. Co-polymerisation of the oxazolines with adipic acid at 160 °C in the bulk resulted in the targeted polyester comb type polymers. The polymers were soluble in a range of organic solvents and compatible with commercial alkyd resins. Model paint formulations containing up to 40 wt% of the linoleyl-based comb polymers exhibited a dramatic reduction in viscosity (from 35 to 13 Poise at 25 °C) with increasing quantities of polymer added. Dynamic mechanical analysis (DMA) studies revealed that the drying rate of the model paint formulations containing the comb polymers was enhanced when compared with that of commercial alkyd resins.

Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures

We have studied the synergetic effect of confinement (carbon nanopore size) and surface chemistry (the number of carbonyl groups) on CO2 capture from its mixtures with CH4 at typical operating conditions for industrial adsorptive separation (298 K and compressed CO2CH4 mixtures). Although both confinement and surface oxidation have an impact on the efficiency of CO2/CH4 adsorptive separation at thermodynamics equilibrium, we show that surface functionalization is the most important factor in designing an efficient adsorbent for CO2 capture. Systematic Monte Carlo simulations revealed that adsorption of CH4 either pure or mixed with CO2 on oxidized nanoporous carbons is only slightly increased by the presence of functional groups (surface dipoles). In contrast, adsorption of CO2 is very sensitive to the number of carbonyl groups, which can be examined by a strong electric quadrupolar moment of CO2. Interestingly, the adsorbed amount of CH4 is strongly affected by the presence of the co-adsorbed CO2. In contrast, the CO2 uptake does not depend on the molar ratio of CH4 in the bulk mixture. The optimal carbonaceous porous adsorbent used for CO2 capture near ambient conditions should consist of narrow carbon nanopores with oxidized pore walls. Furthermore, the equilibrium separation factor was the greatest for CO2/CH4 mixtures with a low CO2 concentration. The maximum equilibrium separation factor of CO2 over CH4 of ∼18–20 is theoretically predicted for strongly oxidized nanoporous carbons. Our findings call for a review of the standard uncharged model of carbonaceous materials used for the modeling of the adsorption separation processes of gas mixtures containing CO2 (and other molecules with strong electric quadrupolar moment or dipole moment).

Solution-free sets for sums of binary forms

In this paper, we obtain quantitative estimates for the asymptotic density of subsets of the integer lattice Z2 that contain only trivial solutions to an additive equation involving binary forms. In the process we develop an analogue of Vinogradov’s mean value theorem applicable to binary forms.

Effect of provenance, plant part and processing on extract profiles from cultivated European Rhodiola rosea L. for medicinal use.

The demand for plant material of Rhodiola rosea L. (Crassulaceae) for medicinal use has increased recently, amid concerns about its quality and sustainability. We have analysed the content of phenylpropanoids (total rosavins) and salidroside in liquid extracts from 3-year old cultivated plants of European origin, and mapped the influence of plant part (rhizome versus root), genotype, drying, cutting, and extraction solvent to chemical composition. Rhizomes contained 1.5-4 times more salidroside (0.3-0.4% dry wt) and total rosavins (1.2-3.0%) than roots. The qualitative decisive phenylpropanoid content in the extracts was most influenced by plant part, solvent, and genotype, while drying temperature and cutting conditions were of less importance. We have shown that R. rosea from different boreal European provenances can be grown under temperate conditions and identified factors to obtain consistent high quality extracts provided that authentic germplasm is used and distinguished between rhizome, roots and their mixtures.

Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations

Novel acid-terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by 1H and 13C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl3, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white-spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans-esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol-functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins.

Antipathogenic activity of probiotics against Salmonella Typhimurium and Clostridium difficile in anaerobic batch culture systems: is it due to synergies in probiotic mixtures or the specificity of single strains?

Probiotics are currently being investigated for prevention of infections caused by enteric pathogens. The aim of this in vitro study was to evaluate the influence of three single probiotics: Lactobacillus casei NCIMB 30185 (PXN 37), Lactobacillus acidophilus NCIMB 30184 (PXN 35), Bifidobacterium breve NCIMB 30180 (PXN 25) and a probiotic mixture containing the above strains plus twelve other strains belonging to the Lactobacillus, Bifidobacterium, Lactococcus, Streptococcus and Bacillus genera on the survival of Salmonella Typhimurium and Clostridium difficile using pH-controlled anaerobic batch cultures containing mixed fecal bacteria. Changes in relevant bacterial groups and effects of probiotic addition on survival of the two pathogens were assessed over 24 h. Quantitative analysis of bacterial populations revealed that there was a significant increase in lactobacilli and/or bifidobacteria numbers, depending on probiotic addition, compared with the control (no added probiotic). There was also a significant reduction in S. Typhimurium and C. difficile numbers in the presence of certain probiotics compared with controls. Of the probiotic treatments, two single strains namely L. casei NCIMB 30185 (PXN 37), and B. breve NCIMB 30180 (PXN 25) were the most potent in reducing the numbers of S. Typhimurium and C. difficile. In addition, the supplementation with probiotics into the systems influenced some fermentations parameters. Acetate was found in the largest concentrations in all vessels and lactate and formate were generally detected in higher amounts in vessels with probiotic addition compared to controls.

Analytical and numerical solutions describing the inward solidification of a binary melt

We present a mathematical model describing the inward solidification of a slab, a circular cylinder and a sphere of binary melt kept below its equilibrium freezing temperature. The thermal and physical properties of the melt and solid are assumed to be identical. An asymptotic method, valid in the limit of large Stefan number is used to decompose the moving boundary problem for a pure substance into a hierarchy of fixed-domain diffusion problems. Approximate, analytical solutions are derived for the inward solidification of a slab and a sphere of a binary melt which are compared with numerical solutions of the unapproximated system. The solutions are found to agree within the appropriate asymptotic regime of large Stefan number and small time. Numerical solutions are used to demonstrate the dependence of the solidification process upon the level of impurity and other parameters. We conclude with a discussion of the solutions obtained, their stability and possible extensions and refinements of our study.

Problems with binary pattern measures for flood model evaluation

As the calibration and evaluation of flood inundation models are a prerequisite for their successful application, there is a clear need to ensure that the performance measures that quantify how well models match the available observations are fit for purpose. This paper evaluates the binary pattern performance measures that are frequently used to compare flood inundation models with observations of flood extent. This evaluation considers whether these measures are able to calibrate and evaluate model predictions in a credible and consistent way, i.e. identifying the underlying model behaviour for a number of different purposes such as comparing models of floods of different magnitudes or on different catchments. Through theoretical examples, it is shown that the binary pattern measures are not consistent for floods of different sizes, such that for the same vertical error in water level, a model of a flood of large magnitude appears to perform better than a model of a smaller magnitude flood. Further, the commonly used Critical Success Index (usually referred to as F<2 >) is biased in favour of overprediction of the flood extent, and is also biased towards correctly predicting areas of the domain with smaller topographic gradients. Consequently, it is recommended that future studies consider carefully the implications of reporting conclusions using these performance measures. Additionally, future research should consider whether a more robust and consistent analysis could be achieved by using elevation comparison methods instead.