Synthesis and Electronic Structure of Dissymmetrical, Naphthalene-Bridged Sandwich Complexes [Cp′Fe(μ‑C10H8)MCp*]x (x = 0, +1; M =Fe, Ru; Cp′ = η5‑C5H2‑1,2,4‑tBu3; Cp* = η5‑C5Me5)

The dissymmetrical naphthalene-bridged complexes [Cp′Fe(μ-C10H8)FeCp*] (3; Cp* = η5-C5Me5, Cp′ = η5-C5H2-1,2,4-tBu3) and [Cp′Fe(μ-C10H8)RuCp*] (4) were synthesized via a one-pot procedure from FeCl2(thf)1.5, Cp′K, KC10H8, and [Cp* FeCl(tmeda)] (tmeda = N,N,N′,N′- tetramethylethylenediamine) or [Cp*RuCl]4, respectively. The symmetrically substituted iron ruthenium complex [Cp*Fe(μ-C10H8)RuCp*] (5) bearing two Cp* ligands was prepared as a reference compound. Compounds 3−5 are diamagnetic and display similar molecular structures, where the metal atoms are coordinated to opposite sides of the bridging naphthalene molecule. Cyclic voltammetry and UV/vis spectroelectrochemistry studies revealed that neutral 3−5 can be oxidized to monocations 3+−5+ and dications 32+−52+. The chemical oxidation of 3 and 4 with [Cp2Fe]PF6 afforded the paramagnetic hexafluorophosphate salts [Cp′Fe(μ-C10H8)FeCp*]PF6 ([3]PF6) and [Cp′Fe(μ-C10H8)RuCp*]PF6 ([4]PF6), which were characterized by various spectroscopic techniques, including EPR and 57Fe Mössbauer spectroscopy. The molecular structure of [4]PF6 was determined by X-ray crystallography. DFT calculations support the structural and spectroscopic data and determine the compositions of frontier molecular orbitals in the investigated complexes. The effects of substituting Cp* with Cp′ and Fe with Ru on the electronic structures and the structural and spectroscopic properties are analyzed.

Selection of potential probiotic lactic acid bacteria from fermented olives by in vitro tests

The present study aims to evaluate the probiotic potential of lactic acid bacteria (LAB) isolated from naturally fermented olives and select candidates to be used as probiotic starters for the improvement of the traditional fermentation process and the production of newly added value functional foods. Seventy one (71) lactic acid bacterial strains (17 Leuconostoc mesenteroides, 1 Ln. pseudomesenteroides, 13 Lactobacillus plantarum, 37 Lb. pentosus, 1 Lb. paraplantarum, and 2 Lb. paracasei subsp. paracasei) isolated from table olives were screened for their probiotic potential. Lb. rhamnosus GG and Lb. casei Shirota were used as reference strains. The in vitro tests included survival in simulated gastrointestinal tract conditions, antimicrobial activity (against Listeria monocytogenes, Salmonella Enteritidis, Escherichia coli O157:H7), Caco-2 surface adhesion, resistance to 9 antibiotics and haemolytic activity. Three (3) Lb. pentosus, 4 Lb. plantarum and 2 Lb. paracasei subsp. paracasei strains demonstrated the highest final population (>8 log cfu/ml) after 3 h of exposure at low pH. The majority of the tested strains were resistant to bile salts even after 4 h of exposure, while 5 Lb. plantarum and 7 Lb. pentosus strains exhibited partial bile salt hydrolase activity. None of the strains inhibited the growth of the pathogens tested. Variable efficiency to adhere to Caco-2 cells was observed. This was the same regarding strains' susceptibility towards different antibiotics. None of the strains exhibited β-haemolytic activity. As a whole, 4 strains of Lb. pentosus, 3 strains of Lb. plantarum and 2 strains of Lb. paracasei subsp. paracasei were found to possess desirable in vitro probiotic properties similar to or even better than the reference probiotic strains Lb. casei Shirota and Lb. rhamnosus GG. These strains are good candidates for further investigation both with in vivo studies to elucidate their potential health benefits and in olive fermentation processes to assess their technological performance as novel probiotic starters.

Spectral design of temperature-invariant narrow bandpass filters for the mid-infrared

The ability of narrow bandpass filters to discriminate wavelengths between closely-separated gas absorption lines is crucial in many areas of infrared spectroscopy. As improvements to the sensitivity of infrared detectors enables operation in uncontrolled high-temperature environments, this imposes demands on the explicit bandpass design to provide temperature-invariant behavior. The unique negative temperature coefficient (dn/dT<0) of Lead-based (Pb) salts, in combination with dielectric materials enable bandpass filters with exclusive immunity to shifts in wavelength with temperature. This paper presents the results of an investigation into the interdependence between multilayer bandpass design and optical materials together with a review on invariance at elevated temperatures.

Effect of seasonal variation on some physical properties and heat stability of milk subjected to ultra-high temperature and in-container sterilisation

Heat stability was evaluated in bulk raw milk, collected throughout the year and subjected to ultra-high temperature (UHT) or in-container sterilisation, with and without added calcium chloride (2 mM), disodium hydrogen phosphate (DSHP, 10 mM) and trisodium citrate (TSC, 10 mM). More sediment was observed following in-container sterilisation (0.24%) compared with UHT (0.19%). Adding CaCl2 made the milk more unstable to UHT than to in-container sterilisation, while adding DSHP and TSC made the milk more unstable during in-container sterilisation than to UHT processing, although TSC addition increased the sediment formed by UHT processing. Better heat stability was observed in autumn and winter than in spring and summer following UHT. However, following in-container sterilisation, samples with added stabilising salts showed significantly improved heat stability in autumn, whereas with added CaCl2, the best heat stability was observed in spring. No correlation was found between urea and heat stability. DSHP and TSC made the milk more unstable during in-container sterilisation than to UHT processing, although TSC addition increased the sediment formed by UHT processing. Better heat stability was observed in autumn and winter than in spring and summer following UHT. However, following in-container sterilisation, samples with added stabilising salts showed significantly improved heat stability in autumn, whereas with added CaCl2, the best heat stability was observed in spring. No correlation was found between urea and heat stability.

Staphylococcus aureus MnhF mediates cholate efflux and facilitates survival under human colonic conditions

Resistance to the innate defences of the intestine is crucial for the survival and carriage of Staphylococcus aureus, a common coloniser of the human gut. Bile salts produced by the liver and secreted into the intestines are one such group of molecules with potent anti-microbial activity. The mechanisms by which S. aureus is able to resist such defences in order to colonize and survive in the human gut are unknown. Here we show that mnhF confers resistance to bile salts, which can be abrogated by efflux pump inhibitors. MnhF mediates efflux of radiolabelled cholic acid in both S. aureus and when heterologously expressed in Escherichia coli, rendering them resistant. Deletion of mnhF attenuated survival of S. aureus in an anaerobic three stage continuous culture model of the human colon (gut model), which represent different anatomical areas of the large intestine.

A sustainable agricultural landscape for Australia: A review of interlacing carbon sequestration, biodiversity and salinity management in agroforestry systems

Transformation of the south-western Australian landscape from deep-rooted woody vegetation systems to shallow-rooted annual cropping systems has resulted in the severe loss of biodiversity and this loss has been exacerbated by rising ground waters that have mobilised stored salts causing extensive dry land salinity. Since the original plant communities were mostly perennial and deep rooted, the model for sustainable agriculture and landscape water management invariably includes deep rooted trees. Commercial forestry is however only economical in higher rainfall (>700 mm yr−1) areas whereas much of the area where biodiversity is threatened has lower rainfall (300–700 mm yr−1). Agroforestry may provide the opportunity to develop new agricultural landscapes that interlace ecosystem services such as carbon mitigation via carbon sequestration and biofuels, biodiversity restoration, watershed management while maintaining food production. Active markets are developing for some of these ecosystem services, however a lack of predictive metrics and the regulatory environment are impeding the adoption of several ecosystem services. Nonetheless, a clear opportunity exists for four major issues – the maintenance of food and fibre production, salinisation, biodiversity decline and climate change mitigation – to be managed at a meaningful scale and a new, sustainable agricultural landscape to be developed.

Terrestrial exposure of oilfield flowline additives diminish soil structural stability and remediative microbial function

Onshore oil production pipelines are major installations in the petroleum industry, stretching many thousands of kilometres worldwide which also contain flowline additives. The current study focuses on the effect of the flowline additives on soil physico-chemical and biological properties and quantified the impact using resilience and resistance indices. Our findings are the first to highlight deleterious effect of flowline additives by altering some fundamental soil properties, including a complete loss of structural integrity of the impacted soil and a reduced capacity to degrade hydrocarbons mainly due to: (i) phosphonate salts (in scale inhibitor) prevented accumulation of scale in pipelines but also disrupted soil physical structure; (ii) glutaraldehyde (in biocides) which repressed microbial activity in the pipeline and reduced hydrocarbon degradation in soil upon environmental exposure; (iii) the combinatory effects of these two chemicals synergistically caused severe soil structural collapse and disruption of microbial degradation of petroleum hydrocarbons.

Effects of aluminium chloride and aluminium chlorohydrate on DNA repair in MCF10A immortalised non-transformed human breast epithelial cells

Use of underarm aluminium (Al)-based antiperspirant salts may be a contributory factor in breast cancer development. At the 10th Keele meeting, Al was reported to cause anchorage-independent growth and double strand DNA breaks in MCF10A immortalised non-transformed human breast epithelial cells. We now report that exposure of MCF10A cells to Al chloride or Al chlorohydrate also compromised DNA repair systems. Longterm (19–21 weeks) exposure to Al chloride or Al chlorohydrate at a 10−4 M concentration resulted in reduced levels of BRCA1 mRNA as determined by real-time RT-PCR and BRCA1 protein as determined by Western immunoblotting. Reduced levels of mRNA for other DNA repair genes (BRCA2, CHK1, CHK2, Rad51, ATR) were also observed using real-time RT-PCR. Loss of BRCA1 or BRCA2 gene function has long been associated with inherited susceptibility to breast cancer but these results suggest that exposure to aluminium-based antiperspirant salts may also reduce levels of these key components of DNA repair in breast epithelial cells. If Al can not only damage DNA but also compromise DNA repair systems, then there is the potential for Al to impact on breast carcinogenesis.

Efficient access to conjugated 4,4’-bipyridinium oligomers using the Zincke reaction: synthesis, spectroscopic and electrochemical properties

The cyclocondensation reaction between rigid, electron-rich aromatic diamines and 1,1′-bis(2,4-dinitrophenyl)-4,4′-bipyridinium (Zincke) salts has been harnessed to produce a series of conjugated oligomers containing up to twelve aromatic/heterocyclic residues. These oligomers exhibit discrete, multiple redox processes accompanied by dramatic changes in electronic absorption spectra.

Effect of impurities in biodiesel-derived waste glycerol on the performance and feasibility of biotechnological processes

The rapid development of biodiesel production technology has led to the generation of tremendous quantities of glycerol wastes, as the main by-product of the process. Stoichiometrically, it has been calculated that for every 100 kg of biodiesel, 10 kg of glycerol are produced. Based on the technology imposed by various biodiesel plants, glycerol wastes may contain numerous kinds of impurities such as methanol, salts, soaps, heavy metals and residual fatty acids. This fact often renders biodiesel-derived glycerol unprofitable for further purification. Therefore, the utilization of crude glycerol though biotechnological means represents a promising alternative for the effective management of this industrial waste. This review summarizes the effect of various impurities-contaminants that are found in biodiesel-derived crude glycerol upon its conversion by microbial strains in biotechnological processes. Insights are given concerning the technologies that are currently applied in biodiesel production, with emphasis to the impurities that are added in the composition of crude glycerol, through each step of the production process. Moreover, extensive discussion is made in relation with the impact of the nature of impurities upon the performances of prokaryotic and eukaryotic microorganisms, during crude glycerol bioconversions into a variety of high added-value metabolic products. Finally, aspects concerning ways of crude glycerol treatment for the removal of inhibitory contaminants as reported in the literature are given and comprehensively discussed

Aluminium and the human breast

The human population is exposed to aluminium (Al) from diet, antacids and vaccine adjuvants, but frequent application of Al-based salts to the underarm as antiperspirant adds a high additional exposure directly to the local area of the human breast. Coincidentally the upper outer quadrant of the breast is where there is also a disproportionately high incidence of breast cysts and breast cancer. Al has been measured in human breast tissues/fluids at higher levels than in blood, and experimental evidence suggests that at physiologically relevant concentrations, Al can adversely impact on human breast epithelial cell biology. Gross cystic breast disease is the most common benign disorder of the breast and evidence is presented that Al may be a causative factor in formation of breast cysts. Evidence is also reviewed that Al can enable the development of multiple hallmarks associated with cancer in breast cells, in particular that it can cause genomic instability and inappropriate proliferation in human breast epithelial cells, and can increase migration and invasion of human breast cancer cells. In addition, Al is a metalloestrogen and oestrogen is a risk factor for breast cancer known to influence multiple hallmarks. The microenvironment is established as another determinant of breast cancer development and Al has been shown to cause adverse alterations to the breast microenvironment. If current useage patterns of Al-based antiperspirant salts contribute to causation of breast cysts and breast cancer, then reduction in exposure would offer a strategy for prevention, and regulatory review is now justified.

Immunological parameters related to the adjuvant effect of the ordered mesoporous silica SBA-15

In 2006, the first report of a nanostructured material as adjuvant was described establishing the effectiveness of the ordered mesoporous SBA-15 silica as an immune adjuvant. The present study evaluated the SBA-15 capacity to modulate the immune responsiveness of High and Low responder mice immunized with BSA encapsulated/adsorbed in SBA-15 by the intramuscular or oral route and the adjuvant effect was compared with the responsiveness induced by BSA in aluminum hydroxide salts or emulsified in Incomplete Freund adjuvant. These results demonstrate the ability of the non-toxic SBA-15 nanoparticles to increase the immunogenicity and repair the responsiveness of the constitutively low responder individuals inducing both the IgG2a and the IgG1 isotypes, independently of the immune cell committed and conditioning the low phenotype. This new adjuvant may reveal novel therapeutic targets for immune modulation and vaccine design. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis and characterization of NiMn(2)O(4) nanoparticles using gelatin as organic precursor

Nanoparticles of NiMn(2)O(4) were successfully obtained by mixing gelatin and inorganic salts NiCl(2) center dot 6H(2)O and MnCl(2) center dot 4H(2)O in aqueous solution. The mixture has been synthesized at different temperatures and resulted in NiMn(2)O(4) nanoparticles with crystallites size in the range of 14-44 nm, as inferred from X-ray powder diffraction (XRPD) data. We have also observed that both the average crystallite size and the unit cell parameters increase with increasing synthesis temperature. Magnetic measurements confirmed the presence of a magnetic transition near 110K. (C) 2008 Published by Elsevier B.V.

Magnetic Fluids Based on gamma-Fe(2)O(3) and CoFe(2)O(4) Nanoparticles Dispersed in Ionic Liquids

The disclosure of magnetic ionic liquids (MILs) as stable dispersions of surface modified gamma-Fe(2)O(3) or CoFe(2)O(4) nanoparticles (NPs) in the 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIBF(4)) ionic liquid is reported. The magnetic NPs were characterized by X-ray powder diffraction, transmission electron microscopy, and Raman spectroscopy. The surface modified NPs have proved to form stable dispersions in BMIBF(4) in the absence of water and behave like a magnetic ionic liquid. The MILs have been characterized by Raman spectroscopy, magnetic measurements, and DSC. The stability of the magnetic NPs in BMIBF(4) is consistently explained by assuming the formation of a semiorganized protective layer composed of supramolecular aggregates in the form of [(BMI)(2)(BF(4))(3)](-). A superparamagnetic behavior and saturation magnetization of ca. 18 emu/g for a sample containing 30% w/w maghemite NPs/BMIBF(4) have been inferred from static and dynamic magnetic measurements. DSC results have shown that the MIL composed of 30% w/w CoFe(2)O(4) NPs/BMIBF(4) remains a liquid phase down to -84 degrees C.

Influence from the sulfonate group (RSO(3)(-)) on the conversion process and emission efficiency of poly(p-phenylene vinylene)

The discovery of an alternative route to convert poly(xylyliden tetrahydrothiophenium chloride) (PTHT) into poly(p-phenylene vinylene) (PPV) using dodecylbenzenesulfonate (DBS) has allowed the formation of ultrathin films with unprecedented control of architecture and emission properties. In this work, we show that this route may be performed with several sufonated compounds where RSO(3)(-) replaces the counter-ion (Cl(-)) of PTHT, some of which are even more efficient than DBS. Spin-coating films were produced from PTHT and azo-dye molecules, an azo-polymer and organic salts as counter-ions of PTHT. The effects of the thermal annealing step of PTHT/RSO(3)(-) films at 110 and 230 degrees C were monitored by measuring the absorption and emission spectra. The results indicate that the exchange of the counterion Cl(-) of PTHT by a linear long chain with RSO(3)(-) group is a general procedure to obtain PPV polymer at lower conversion temperature (ca. 110 degrees C) with significant increase in the emission efficiency, regardless of the chemical position and the number of sulfonate groups. With the enhanced emission caused by Congo Red and Tinopal as counter-ions, it is demonstrated that the new synthetic route is entirely generic, which may allow accurate control of conversion and emission properties. (C) 2010 Elsevier B.V. All rights reserved.