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1.
Chem Commun (Camb) ; 53(3): 647-650, 2017 01 03.
Article in English | MEDLINE | ID: mdl-27990535

ABSTRACT

A repulsive double layer force has been measured for ethylammonium nitrate (EAN) at 373 K and 393 K, which is absent at lower temperatures. This temperature-tuneable change in behaviour is the opposite of recent observations which challenge traditional views of ionicity. This finding thus widens the debate about the very nature of ionic liquids.

2.
Phys Chem Chem Phys ; 18(34): 23657-62, 2016 Aug 24.
Article in English | MEDLINE | ID: mdl-27511143

ABSTRACT

Atomic force microscopy (AFM) reveals that tribotronic control of friction using an external potential applied to a gold surface is possible for ionic liquid (IL) concentrations as low as 5 mol% in hexadecane. The IL used is trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate, in which both the cation and anion have surfactant-like structures, and is miscible with hexadecane in all proportions. For IL concentrations less than 5 mol% friction does not vary with applied potential, but for 5 mol% and above changing the potential changes the composition of the IL boundary layer from cation-enriched (negative potentials) to anion-enriched (positive potentials). As the lubricities of the cation-rich and anion-rich boundary layers differ, this enables active control of friction in oil-based lubricants.

3.
Phys Chem Chem Phys ; 17(24): 16047-52, 2015 Jun 28.
Article in English | MEDLINE | ID: mdl-26027558

ABSTRACT

The energetic origins of the variation in friction with potential at the propylammonium nitrate-graphite interface are revealed using friction force microscopy (FFM) in combination with quantum chemical simulations. For boundary layer lubrication, as the FFM tip slides energy is dissipated via (1) boundary layer ions and (2) expulsion of near-surface ion layers from the space between the surface and advancing tip. Simulations reveal how changing the surface potential changes the ion composition of the boundary and near surface layer, which controls energy dissipation through both pathways, and thus the friction.

4.
J Colloid Interface Sci ; 430: 56-60, 2014 Sep 15.
Article in English | MEDLINE | ID: mdl-24998054

ABSTRACT

Steady shear viscosity measurements have been performed on 100 kDa poly(ethylene oxide) (PEO) dissolved in the protic ionic liquids ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) and in water. The zero shear viscosity in all three solvents increases with polymer concentration, falling into three concentration regimes corresponding to dilute, semi-dilute and network solutions. Huggins plots reveal three distinct solvent conditions: good (water), good-theta (EAN) and theta (PAN). However, differences in the transition concentrations, power law behaviour of the viscosities, and relaxation times arising from shear thinning in the two ILs can be directly related to the effects of solvent nanostructure.


Subject(s)
Ionic Liquids/chemistry , Polyethylene Glycols/chemistry , Quaternary Ammonium Compounds/chemistry , Viscosity
5.
Proc Natl Acad Sci U S A ; 101(30): 11105-10, 2004 Jul 27.
Article in English | MEDLINE | ID: mdl-15263089

ABSTRACT

The bacterial family Enterobacteriaceae is notable for its well studied human pathogens, including Salmonella, Yersinia, Shigella, and Escherichia spp. However, it also contains several plant pathogens. We report the genome sequence of a plant pathogenic enterobacterium, Erwinia carotovora subsp. atroseptica (Eca) strain SCRI1043, the causative agent of soft rot and blackleg potato diseases. Approximately 33% of Eca genes are not shared with sequenced enterobacterial human pathogens, including some predicted to facilitate unexpected metabolic traits, such as nitrogen fixation and opine catabolism. This proportion of genes also contains an overrepresentation of pathogenicity determinants, including possible horizontally acquired gene clusters for putative type IV secretion and polyketide phytotoxin synthesis. To investigate whether these gene clusters play a role in the disease process, an arrayed set of insertional mutants was generated, and mutations were identified. Plant bioassays showed that these mutants were significantly reduced in virulence, demonstrating both the presence of novel pathogenicity determinants in Eca, and the impact of functional genomics in expanding our understanding of phytopathogenicity in the Enterobacteriaceae.


Subject(s)
Genome, Bacterial , Pectobacterium carotovorum/genetics , Pectobacterium carotovorum/pathogenicity , Plant Diseases/microbiology , Solanum tuberosum/microbiology , Virulence/genetics , Base Sequence , Biological Evolution , DNA Primers , Environment , Molecular Sequence Data , Polymerase Chain Reaction
6.
J Colloid Interface Sci ; 266(2): 236-44, 2003 Oct 15.
Article in English | MEDLINE | ID: mdl-14527445

ABSTRACT

The equilibrium and kinetic aspects of the adsorption of alkyltrimethylammonium surfactants at the silica-aqueous solution interface have been investigated using optical reflectometry. The effect of added electrolyte, the length of the hydrocarbon chain, and of the counter- and co-ions has been elucidated. Increasing the length of the surfactant hydrocarbon chain results in the adsorption isotherm being displaced to lower concentrations. The adsorption kinetics indicate that above the cmc micelles are adsorbing directly to the surface and that as the chain length increases the hydrophobicity of the surfactant has a greater influence on the adsoption kinetics. While the addition of 10 mM KBr increases the CTAB maximal surface excess, there is no corresponding increase for the addition of 10 mM KCl to the CTAC system. This is attributed to the decreased binding efficiency of the chloride ion relative to the bromide ion. Variations in the co-ion species (Li, Na, K) have little effect on the adsorption rate and surface excess of CTAC up to a bulk electrolyte concentration of 10 mM. However, the rate of adsorption is increased in the presence of electrolyte. Slow secondary adsorption is seen over a range of concentrations for CTAC in the absence of electrolyte and importantly in the presence of LiCl; the origin of this slow adsorption is attributed to a structural barrier to adsorption.

7.
Adv Colloid Interface Sci ; 103(3): 219-304, 2003 May 30.
Article in English | MEDLINE | ID: mdl-12781966

ABSTRACT

Until recently, the rapid time scales associated with the formation of an adsorbed surfactant layer at the solid-aqueous interface has prevented accurate investigation of adsorption kinetics. This has led to the mechanism of surfactant adsorption being inferred from thermodynamic data. These explanations have been further hampered by a poor knowledge of the equilibrium adsorbed surfactant morphology, with the structure often misinterpreted as simple monolayers or bilayers, rather than the discrete surface aggregates that are present in many surfactant-substrate systems. This review aims to link accepted equilibrium data with more recent kinetic and structural information in order to describe the adsorption process for ionic surfactants. Traditional equilibrium data, such as adsorption isotherms obtained from depletion approaches, and the most popular methods by which these data are interpreted are examined. This is followed by a description of the evidence for discrete aggregation on the substrate, and the morphology of these aggregates. Information gained using techniques such as atomic force microscopy, fluorescence quenching and neutron reflectivity is then reviewed. With this knowledge, the kinetic data obtained from relatively new techniques with high temporal resolution, such as ellipsometry and optical reflectometry, are examined. On this basis the likely mechanisms of adsorption are proposed.


Subject(s)
Colloids/chemistry , Solutions/chemistry , Water/chemistry , Adsorption , Calorimetry/methods , Electrochemistry/methods , Kinetics , Magnetic Resonance Spectroscopy/methods , Microscopy, Atomic Force/methods , Microscopy, Interference/methods , Spectrometry, Fluorescence/methods , Static Electricity , Surface Properties , Surface-Active Agents/chemistry , Wetting Agents/chemistry
8.
Nature ; 419(6906): 527-31, 2002 Oct 03.
Article in English | MEDLINE | ID: mdl-12368867

ABSTRACT

Since the sequencing of the first two chromosomes of the malaria parasite, Plasmodium falciparum, there has been a concerted effort to sequence and assemble the entire genome of this organism. Here we report the sequence of chromosomes 1, 3-9 and 13 of P. falciparum clone 3D7--these chromosomes account for approximately 55% of the total genome. We describe the methods used to map, sequence and annotate these chromosomes. By comparing our assemblies with the optical map, we indicate the completeness of the resulting sequence. During annotation, we assign Gene Ontology terms to the predicted gene products, and observe clustering of some malaria-specific terms to specific chromosomes. We identify a highly conserved sequence element found in the intergenic region of internal var genes that is not associated with their telomeric counterparts.


Subject(s)
DNA, Protozoan , Plasmodium falciparum/genetics , Animals , Base Sequence , Chromosomes , Genes, Protozoan , Genome, Protozoan , Molecular Sequence Data , Multigene Family , Proteome , Protozoan Proteins/genetics , Sequence Analysis, DNA
10.
Acad Manage Rev ; 3(1): 119-28, 1978 Jan.
Article in English | MEDLINE | ID: mdl-10307178

ABSTRACT

A number of theoretical problems exist which underline the development and implementation of behaviorally anchored rating scales in particular and all performance evaluation procedures in general. Several specific areas need additional study. It is concluded that future research should concentrate on the process of performance evaluation in the framework of a cognitive, information-processing model of the rater.


Subject(s)
Behavior , Employee Performance Appraisal , Personnel Management , Humans , Psychology, Industrial
12.
Biochem J ; 107(3): 361-6, 1968 Apr.
Article in English | MEDLINE | ID: mdl-5650363

ABSTRACT

1. Changes in nucleic acid metabolism in first seedling leaves of barley plants during aging (from 7 to 27 days) were followed, and the effect of continual removal of the second leaf and basal meristem or of treating the first leaf with 20p.p.m. kinetin on these changes was examined. During aging of the first seedling leaves the ribosomal RNA, DNA and soluble RNA declined, with ribosomal RNA showing the most rapid fall. This was, however, accompanied by increased incorporation of (32)P into RNA, which reached its peak on the fifteenth day. 2. Second-leaf removal partially suppressed first-leaf senescence as judged by retarded chlorophyll and nucleic acid decline and by a decreased extent of RNA labelling. Treatment with kinetin, however, did not prove effective. 3. No significant differences in the sucrose-gradient pattern of (32)P-labelled nucleic acids or in the (32)P-labelled nucleotide composition of RNA fractions during aging or during the two treatments were noted, except for a decrease in CMP content of soluble RNA during aging. 4. The results demonstrate that important changes in RNA metabolism are associated with leaf senescence.


Subject(s)
DNA/metabolism , Edible Grain/metabolism , Plant Growth Regulators/pharmacology , RNA, Transfer/metabolism , RNA/metabolism , Aging , Centrifugation, Density Gradient , Chlorophyll/metabolism , Cytosine Nucleotides/metabolism , Edible Grain/growth & development , Phosphorus/metabolism , Phosphorus Isotopes , RNA/biosynthesis , Ribosomes/metabolism
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