Chlorometallate(III) ionic liquids as Lewis acidic catalysts - a quantitative study of acceptor properties

The Gutmann Acceptor Number (AN), which is a quantitative measure of Lewis acidity, has been estimated using the P-31 NMR chemical shift of a probe molecule, triethylphosphine oxide, for a range of chlorometallate(III) ionic liquids, based on Group 13 metals (aluminium(III), gallium(III) and indium(III)) and the 1-octyl-3-methylimidazolium cation, at different compositions. The results were interpreted in terms of extant speciation studies of chlorometallate(III) ionic liquids, and compared with a range of standard molecular solvents and acids. The value of these data were illustrated in terms of the selection of appropriate ionic liquids for specific applications.

The effect of various treatment conditions on natural zeolites: Ion exchange, acidic, thermal and steam treatments

Two different natural zeolites having different phase compositions were obtained from different regions of Turkey and modified by ion-exchange (0.5 M NH4NO3) and acid leaching using 1 M HCl. The natural and modified samples were treated at low temperature (LT), high temperature (HT) and steam (ST) conditions and characterised by XRF, XRD, BET, FTIR, DR-UV-Vis, NH3-TPD and TGA. Ion-exchange with NH4+ of natural zeolites results in the exchange of the Na+ and Ca2+ cations and the partial exchange of the Fe3+ and Mg2+ cations. However, steam and acidic treatments cause significant dealumination and decationisation, as well as loss of crystalline, sintering of phases and the formation of amorphous material. The presence of mordenite and quartz phases in the natural zeolites increases the stability towards acid treatment, whereas the structure of clinoptilolite-rich zeolites is mostly maintained after high temperature and steam treatments. The natural and modified zeolites treated at high temperature and in steam were found to be less stable compared with synthetic zeolites, resulting in a loss of crystallinity, a decrease in the surface area and pore volume, a decrease in the surface acidity as well as dealumination, and decationisation. (C) 2012 Elsevier Inc. All rights reserved.

Burkholderia cepacia complex isolates survive intracellularly without replication within acidic vacuoles of Acanthamoeba polyphaga

We have previously demonstrated that isolates of the Burkholderia cepacia complex can survive intracellularly in murine macrophages and in free-living Acanthamoeba. In this work, we show that the clinical isolates B. vietnamiensis strain CEP040 and B. cenocepacia H111 survived but did not replicate within vacuoles of A. polyphaga. B. cepacia-containing vacuoles accumulated the fluid phase marker Lysosensor Blue and displayed strong blue fluorescence, indicating that they had low pH. In contrast, the majority of intracellular bacteria within amoebae treated with the V-ATPse inhibitor bafilomycin A1 localized in vacuoles that did not fluoresce with Lysosensor Blue. Experiments using bacteria fluorescently labelled with chloromethylfluorescein diacetate demonstrated that intracellular bacteria remained viable for at least 24 h. In contrast, Escherichia coli did not survive within amoebae after 2 h post infection. Furthermore, intracellular B. vietnamiensis CEP040 retained green fluorescent protein within the bacterial cytoplasm, while this protein rapidly escaped from the cytosol of phagocytized heat-killed bacteria into the vacuolar lumen. Transmission electron microscopy analysis confirmed that intracellular Burkholderia cells were structurally intact. In addition, both Legionella pneumophila- and B. vietnamiensis-containing vacuoles did not accumulate cationized ferritin, a compound that localizes within the lysosome. Thus, our observations support the notion that B. cepacia complex isolates can use amoebae as a reservoir in the environment by surviving without intracellular replication within an acidic vacuole that is distinct from the lysosomal compartment.

Acidic properties of nanolayered ZSM-5 zeolites

The acidic properties of nanolayered ZSM-5 zeolites synthesized with the aid of multiquaternary ammonium surfactants were investigated in detail. A substantial fraction of Al is present in highly dispersed form at extraframework positions indicative of the defective nature of the calcined nanolayered zeolites. Acidity characterization reveals that the Brønsted acid sites are similar in strength to those in bulk HZSM-5. Nanolayered zeolites contain a higher amount of Brønsted acid sites (BAS) at their external (mesopore) surface. Unilamellar zeolites have a higher concentration of external BA and silanol sites than multilamellar ones. The number of BAS in the nanolayered zeolites is considerably lower than the tetrahedral Al content, the difference increasing with nanolayer thickness. Except for one particular sample (nanolayered ZSM-5 synthesized from COH template), the total turnover of methanol normalized per BAS trends inversely with the concentration of BAS. There is no correlation with the concentration of external BAS. Catalyst deactivation due to coke mainly depends on the BAS concentration. A unilamellar ZSM-5 zeolite prepared using COH displayed substantially improved performance in terms of a much lower rate of coke deactivation in line with earlier data Choi et al. [10]. Since the acidic and textural properties of this zeolite did not differ significantly from the others, it remains to be determined why this zeolite performs so much better. © 2013 Elsevier Ltd. All rights reserved.

A Recyclable Acidic Ionic Liquid Gel Catalyst for Dehydration: Comparison with an Analogous SILP Catalyst.

An acid-functionalized ionic liquid was entrapped within a silica gel to yield a recyclable liquid phase catalyst for the dehydration of rac-1-phenyl ethanol. Hot filtration tests showed that the activity was within the gel. Comparison with an analogous SILP system revealed fundamental differences in the properties and behavior of the materials.

A role for whey acidic protein four-disulfide-core 12 (WFDC12) in the regulation of the inflammatory response in the lung

Introduction: Secretory leucocyte protease inhibitor and elafin are members of the whey acidic protein (WAP), or WAP four disulfide-core (WFDC), family of proteins and have multiple contributions to innate defence including inhibition of neutrophil serine proteases and inhibition of the inflammatory response to lipopolysaccharide (LPS). This study aimed to explore potential activities of WFDC12, a previously uncharacterised WFDC protein expressed in the lung. Methods: Recombinant expression and purification of WFDC12 were optimised in Escherichia coli. Antiprotease, antibacterial and immunomodulatory activities of recombinant WFDC12 were evaluated and levels of endogenous WFDC12 protein were characterised by immunostaining and ELISA. Results: Recombinant WFDC12 inhibited cathepsin G, but not elastase or proteinase-3 activity. Monocytic cells pretreated with recombinant WFDC12 before LPS stimulation produced significantly lower levels of the pro-inflammatory cytokines interleukin-8 and monocyte chemotactic protein-1 compared with cells stimulated with LPS alone. Recombinant WFDC12 became conjugated to fibronectin in a transglutaminase-mediated reaction and retained antiprotease activity. In vivo WFDC12 expression was confirmed by immunostaining of human lung tissue sections. WFDC12 levels in human bronchoalveolar lavage fluid from healthy and lung-injured patients were quantitatively compared, showing WFDC12 to be elevated in both patients with acute respiratory distress syndrome and healthy subjects treated with LPS, relative to healthy controls. Conclusions: Together, these results suggest a role for this lesser known WFDC protein in the regulation of lung inflammation.

Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water

Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry.

Developmental expression of glial fibrillary acidic protein and glutamine synthetase in serum-free aggregating cell cultures of fetal rat telencephalon.

Serum-free aggregating cell cultures of fetal rat telencephalon were examined by a combined biochemical and double-labeling immunocytochemical study for the developmental expression of glial fibrillary acidic protein (GFAP) and glutamine synthetase (GS). It was found that these two astroglial markers are co-expressed at different developmental stages in vitro. During the phase of cellular maturation (i.e. between days 14 and 34), GFAP levels and GS activity increase rapidly and in parallel. At the same time, the number of immunoreactive cells increase while the long and thick processes staining in early cultures gradually disappear. The present results demonstrate that in this particular cell culture system only one type of astrocytes develops which expresses both GFAP and GS and which attains a relatively high degree of maturation.

Skeletal muscle fibre-type comparison of whole tissue and subcellular membrane phospholipids and fatty acids

Membranes are dynamic structures that affect cell structure and function. Compositional changes ofmembranes have been shown with the application of a perturbation; however these are limited to whole tissue analysis. The purpose of this thesis was to compare the phospholipid (PL) fatty acid (FA) composition of rat whole muscle (Wm) to 1) purified and non-purified subsarcolemmal (SS) mitochondria in soleus, plantaris, and red gastrocnemius, and 2) sarcolemma, transverse-tubules, SS and intermyofibrillar (IMF) mitochondria fix)m whole hindlimb. The major findings were that 1) contamination significantly altered the PL FA composition of the SS mitochondrial membrane fraction, 2) Wm and SS mitochondria compositions differed between muscle types, and 3) Wm did not accurately reflect the PL FA composition of any isolated subcellular membranes, with each being unique from each other. As such, the relevancy of the trends reported in the literature of the effects of perturbations on Wm may be limited.

Effect of the position of the double-bond in monounsaturated phospholipids on the dynamics of model membranes

Therllloelynalllics of lllodel 11lel1ll)rane systeills containing 1110nollnsaturatecl I)lloSI)holil) ids is strongly infllienced l)y the I)osition of the C==C dOlll)le })ond in tIle acyl chain. The telllI)eratllres of both chain-nlelting (TM) and La -+ HI! (TH) I)hase traIlsitions are lowered by IIp to 20°C when C==C is Inoved froln positions 6 or 11 to I)osition 9 in an 18-carl)on chain. This work is an attellll)t to ellicidate the uIlderlying Illoleclilar Illechanisllls reSI)Onsi])le for tllese draillatic tllerillodynaillic changes. Mixtllres of di-18: 1 l)hoSI)hatidylethanolanline with C==C at l)ositioIlS 6, 9, 11 were llsed, witll a sI1lall aI1lOlint of I)erdellterated tetradecanol, known to })e a gooel rel)Orter of the cllain Illoleclilar order. SI)ectral second 11I0I1lents were llsed to Illonitor tIle La -+ HII I)hase transition, which was fOllnd to ])e ])road (2-6°C), with a slight llysteresis on heatiIlg/cooling. The orientational order I)rofiles were nleasllred 1lSiIlg 2H Illiclear Illagnetic resonance and changes in these order I)rofiles between La aIld HII I)hases silow l)oth a local increase in order in the vicinity of the C==C bonds and an o\Terall decrease ill the average orientational order of the chain as a whole. These Sll])tle changes recluire })oth high-fidelity SI)ectrosCol)y and a careflll data analysis that takes into aCCOllnt the effects due to l)artiall1lagnetically-indllced orientational ordering of the l)ilayers. In tIle COIltext of SOllle recently rel)Orted cross-relaxation 11leaSlirenlents in Silllilar l)llOSI)llolil)iels, 0111' reslilts sllggest that large-anll)litllde conforlllational changes in the interior of tIle I110del 111eI11])ranes I)lay a 1110re significant role than I)reviollsly thOllght.

Measurement of forces between and within bilayers of neutral phospholipids

Phospholipids in water form lamellar phases made up of alternating layers of water and bimolecular lipid leaflets. Three complementary methods, osmotic, mechanical, and vapour pressures, were used to measure the work of removing water from lamellar phases composed of frozen dipalmitoylphosphatidylcholine ( DPPC ), melted DPPC, egg phosphatidylethanolamine or equimolar mixtures of DPPC and cholesterol ( DPPC/CHOL ), Concurrently the structural changes that resulted from this water removal were measured using X-ray diffraction. The work was divided into that which forces the bilayers together ( F ) and that which compresses the molecules together within the bilayers ( F )# A large repulsive force exists between bilayers composed of each of the lipids studied and this force increases exponentially as bilayer separation is decreased. F is affected by the nature of the head groups, conformation of the acyl chains and heterogeneity of these chains. In general all of the melted phosphatidylcholines ( melted DPPC, egg lecithin and DPPC/CHOL ) have large equilibrium separations in excess water resulting from large repulsive hydration forces between these bilayers. By comparison, egg PE has an increased attractive force, and frozen DPPC has a decreased hydration force; each results in smaller separations in water for these two lipids. The chemical potentials of the water between the bilayers for all these lipids lie on a continuum, indicating that interbilayer water cannot be characterized by two discrete states, usually referred to as "bound" or "non**bound". For all lipids studied a maximum of 25 % of the total work done on the system goes into deforming the bilayers. The method used here viii to separate repulsion from deformation, developed for us by v. A. Parsegian, provides a unique method for the measurement of lateral pressure of a bilayer and its modulus of deformability ( Y ). Lateral pressure is affected by the nature of the head group, conformation and heterogeneity of the acyl chains. For small changes in molecular surface area ( A ) near equilibrium, both melted and frozen DPPC have similar values for the deformability modulus. Thus in this regime it requires about the same force to change the angle of tilt of frozen chains as it does to compress the fluid bilayer. The introduction of cholesterol into bilayers of DPPC reduces dramatically the lateral pressure of the bilayers over a large range of molecular surface areas ( A ). The variation in the magnitude of bilayer repulsion with different phospholipids provides a basis for the mechanism of lipid segregation in mixed lipid systems and suggests that interacting heterogeneous membranes may influence or modulate the composition of the opposing membrane. The measurements of deformabilities of bilayers provides a direct comparison of them with the properties of monolayers.

A Novel Acinetobacter Sp. For 'Treating Highly Acidic Rubber Latex Cen'trifugation Effluent

A novel Acinetobacter sp. BTJR-IO isolated from highly acidic (pH 2.5-4.5) rubber latex centrifugation effluent with high COD (22000 rng/L) and BOD (5000 rng/L). This strain could effect 39.5% COD reduction on free cell inoculation of effluent without incorporation of additional nutrients after 8 days. CalciLnn alginate irrmobilized cells showed 16.4% and 25% COD reduction after 6 hra, without aeration and after 1 hr. with mild aeration under batch process respectively. Whereas 44.0% COD reduction could be achieved after 6 hrs. on continuous treatment in a packed bed reactor with mild aeration. Further, even after 3 cycles 37% COD reduction was recorded with continuous treatment

Displacement of Zn through acidic light-textured soils

In order to gain understanding of the movement of pollutant metals in soil. the chemical mechanisms involved in the transport of zinc were studied. The displacement of zinc through mixtures of sand and cation exchange resin was measured to validate the methods used for soil. With cation exchange capacities of 2.5 and 5.0 cmol(c) kg(-1). 5.6 and 8.4 pore volumes of 10 mM CaCl2, respectively, were required to displace a pulse of ZnCl2. A simple Burns-type model (Wineglass) using an adsorption coefficient (K-d) determined by fitting a straight line relationship to an adsorption isotherm gave a good fit to the data (K-d=0.73 and 1.29 ml g(-1), respectively). Surface and subsurface samples of an acidic sandy loam (organic matter 4.7 and 1.0%. cation exchange capacity (CEC) 11.8 and 6.1 cmol(c) kg(-1) respectively) were leached with 10 mM calcium chloride. nitrate and perchlorate. With chloride. the zinc pulse was displaced after 25 and 5 pore volumes, respectively. The Kd values were 6.1 and 2.0 ml g(-1). but are based on linear relationships fitted to isotherms which are both curved and show hysteresis. Thus. a simple model has limited value although it does give a general indication of rate of displacement. Leaching with chloride and perchlorate gave similar displacement and Kd values, but slower movement occurred with nitrate in both soil samples (35 and 7 pore volumes, respectively) which reflected higher Kd values when the isotherms were measured using this anion (7.7 and 2.8 ml g(-1) respectively). Although pH values were a little hi-her with nitrate in the leachates, the differences were insufficient to suggest that this increased the CEC enough to cause the delay. No increases in pH occurred with nitrate in the isotherm experiments. Geochem was used to calculate the proportions of Zn complexed with the three anions and with fulvic acid determined from measurements of dissolved organic matter. In all cases, more than 91% of the Zn was present as Zn2+ and there were only minor differences between the anions. Thus, there is an unexplained factor associated with the greater adsorption of Zn in the presence of nitrate. Because as little as five pore volumes of solution displaced Zn through the subsurface soil, contamination of ground waters may be a hazard where Zn is entering a light-textured soil, particularly where soil salinity is increased. Reductions in organic matter content due to cultivation will increase the hazard. (C) 2004 Elsevier B.V. All rights reserved.

Effect of pH on the development of acidic sites in clayey and sandy loam Oxisol from the Cerrado Region, Brazil

Titration curves were determined for soil from horizon samples of a clayey and a sandy loam Oxisol by (a) adding NaOH to soil suspensions and (b) incubating moist soils with Ca(OH)(2). The organic fraction was primarily responsible for buffering in both soils. Humic acids were more important than fulvic acids in buffering against NaOH additions. With Ca(OH)(2), greater buffer capacities were found due to carboxyl sites, primarily on fulvic acids, becoming complexed with Ca2+ so that in the clay soil humic and fulvic acids were equally important as buffering components while fulvic acids were more important in the sandy loam soil. The buffer capacity of organic matter against Ca(OH)(2) additions was 1.1 mol(c) kg(-1) pH(-1). In the incubated soils, exchangeable cations were also determined and changes in the amounts of exchangeable and non-exchangeable Ca2+ acidity and effective cation exchange capacity were calculated. Up to half the added Ca2+ became complexed and was nonexchangeable. Aluminum complexed by organic matter appears to be an important buffering component, together with non exchangeable H+. With the increase of pH the dissociated sites from the carboxyl groups could complex Ca2+. (c) 2005 Elsevier B.V. All rights reserved.