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PubMed2005

Morphological specificity of yeast and filamentous Candida albicans forms on surface properties.

Physicochemical surface properties of Candida albicans were assessed from microbial adhesion to human epithelial cells and to octane droplets. The adherence of cells demonstrated the occurrence of morphological specificity for these adhesion assays. Filamentous forms exhibited adherence third times higher compared to budding forms, while their electrophoretic mobilities were comparable. Force measurements performed on filamentous form by AFM demonstrated that such adhesion was associated with microfibrillar surface structure.

Algorithms↗
PubMed2005

The aqueous reference for ESR oximetry.

The interaction of molecular oxygen with derivatives of nitroxide EPR spin labels has been investigated using nuclear spin-relaxation spectroscopy in aqueous and nonaqueous solvents. The proton spin-lattice relaxation rate induced by oxygen provides a measure of the local concentration of oxygen, which we find is dependent on solvent. In water, the hydrophobic effect increases the local concentration of oxygen in the nonpolar portions of solute molecules. For nitroxides reduced to the hydroxylamine in aqueous solutions, we find that the local concentration of oxygen is approximately twice that associated with a free diffusion hard sphere limit, while in octane, this effect is absent. These results show that nitroxide based ESR oximetry may suffer a reference concentration shift of order a factor of two if the aqueous nitroxide spectrum or relaxation is used as the reference.

Chloroform↗
PubMed2006

High resolution non-contact AFM imaging of liquids condensed onto chemically nanopatterned surfaces.

The wetting of ethanol and octane on chemically nanopatterned surfaces has been investigated using Atomic Force Microscopy (AFM) under controlled environmental conditions. The patterns were generated on a methyl-terminated, organic monolayer using an AFM electro-oxidation process. The subsequent wetting of the organic liquids was studied using non-contact mode AFM under equilibrium conditions with the vapor. This study of condensed nanoliquids provides the first reliable measurements of sub 100 nm liquid profile shapes. The derived contact angles give an estimate of the line tension.

Ethanol↗
PubMed2002

Simulations of membranes and other interfacial systems using P2(1) and Pc periodic boundary conditions.

We demonstrate the ease and utility of simulating heterogeneous interfacial systems with P2(1) and Pc periodic boundary conditions which allow, for example, lipids in a membrane to switch leaflets. In preliminary tests, P2(1) was shown to yield equivalent results to P1 in simulations of bulk water, a water/vacuum interface, and pure DPPC bilayers with an equal number of lipids per leaflet; equivalence of Pc and P1 was also demonstrated for the former two systems. P2(1) was further tested in simulations involving the spreading of an octane film on water, and equilibration of a DPPC bilayer from an initial condition containing different numbers of lipids in the two leaflets. Lastly, a simulation in P2(1) of a DOPC/melittin membrane showed significant passage of lipids to the melittin-containing leaflet from the initial distribution, and lends insight into the condensation of lipids by melittin.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2000

Preparation of methyl 2,3-di-O-mesyl-4,6-thioanhydro-alpha-D-galactopyranoside and methyl 2-O-mesyl-4,6-thioanhydro-alpha-D-gulopyranoside.

Two 2-oxa-7-thiabicyclo[4.2.0]octane derivatives, 4 and 10, with the D-galacto and D-gulo configuration, respectively, were obtained from methyl alpha-D-glucopyranoside. The thietane cyclization involved a thio-Mitsunobu reaction resulting in a 6-thioacetate, which underwent selective base-catalyzed intramolecular nucleophilic substitution at a C-4 mesylate. The structures of 4 and 10 were elucidated by X-ray diffraction analysis.

Acetates↗
PubMed1996

Refolding of triosephosphate isomerase in low-water media investigated by fluorescence resonance energy transfer.

The refolding and reassociation of rabbit muscle triosephosphate isomerase (TPI) monomers unfolded with guanidine hydrochloride (GdnHCl) was studied in aqueous media and in reverse micelles (RM) formed with hexadecyltrimethylammonium bromide and n-octane/hexanol. Fluorescence resonance energy transfer (FRET) studies were carried out using TPI labeled at Cys-217 with 5-((2-((iodoacetyl)-amino)ethyl)amino)naphthalene-1-sulfonic acid (1,5-IAEDANS) and TPI labeled at one of the free amino groups with fluorescein 5'-isothiocyanate (FITC). Efficient FRET between monomers of AEDANS-TPI and FITC-TPI in aqueous media was detected 2-3 min after denaturant dilution and remained constant for hours. The distance between AEDANS and FITC in a labeled, renatured hetero-TPI dimer calculated from FRET results was 48 A, in reasonable agreement with estimates based on the crystal structure of TPI. In RM, recovery of enzyme activity during renaturation correlates with the appearance of a high-intrinsic fluorescence intermediate believed to be a partially folded monomer (Fernández-Velasco et al., 1995). Nevertheless, when AEDANS- and FITC-labeled monomers were mixed in RM, FRET occurred as soon as GdnHCl was diluted (FRET efficiency = 0.36), preceding the changes in TPI intrinsic fluorescence and reactivation. Thereafter, the efficiency of FRET increased during the next hour up to approximately 0.50, where it remained after 24 h, when 80% of the enzyme activity was recovered. The high initial FRET seen in RM could indicate the formation of an inactive dimer within the first minutes after denaturant dilution. The further increase in FRET observed over the next hour could reflect conformational rearrangements of the protein and transition from the inactive to the active dimer.

Animals↗
PubMed2005

Unexpected Si:Al effect on the binary mixtures liquid phase adsorption selectivities in faujasite zeolites.

A batch technique was applied to determine the equilibrium adsorption of benzene from its benzene/octane and benzene/octene mixture on NaX (Si:Al 1.20) and NaY (Si:Al 2.79) in liquid phase. Benzene was preferentially adsorbed from both mixtures on NaX and NaY. Regardless whether octane or octene was present in the binary mixture, benzene was adsorbed more selectively on the high-silica NaY compared to NaX, which contained more cations. The presence of cations on the SIII/SIII' site inside the supercages of NaX causes a more difficult hosting of benzene inside the supercages of NaX and especially on the 12-membered ring site. However, at sufficiently high external benzene concentration (>10 mol %), the 12-membered ring site of NaX will be occupied by benzene, leading to a maximum adsorption capacity of five benzenes per supercage on both NaX and NaY. The double bond present inside octene allows the molecules to compete for the adsorption sites with benzene. The competitive effect of octene prevents the fifth benzene molecule to adsorb in the NaX supercage within the investigated concentration range.

Adsorption↗
PubMed2002

Aroma compound analysis of Eruca sativa (Brassicaceae) SPME headspace leaf samples using GC, GC-MS, and olfactometry.

The aroma compounds of rocket salad (Eruca sativa) SPME headspace samples of fresh leaves were analyzed using GC, GC-MS, and olfactometry. More than 50 constituents of the Eruca headspace could be identified to be essential volatiles, responsible for the characteristic intense green; herbal; nutty and almond-like; Brassicaceae-like (direction of cabbage, broccoli, and mustard); and horseradish-like aroma of these salad leaves. As aroma impact compounds, especially isothiocyanates, and derivatives of butane, hexane, octane, and nonane were identified. 4-Methylthiobutyl isothiocyanate (14.2%), cis-3-hexen-1-ol (11.0%), cis-3-hexenyl butanoate (10.8%), 5-methylthiopentyl isothiocyanate (9.3%), cis-3-hexenyl 2-methylbutanoate (5.4%), and 5-methylthiopentanenitrile (5.0%) were found in concentrations higher than 5.0% (calculated as % peak area of GC analysis using a nonpolar column).

Alkanes↗
PubMed2005

Neutral homoaromaticity in some heterocyclic systems.

[reaction: see text] Neutral homoaromaticity has been evaluated in heterocyclic systems related to the bicyclo[3.2.1]octane skeleton with replacement of CH(2) at C-2 in bicyclo[3.2.1]octa-3,6-diene with X = BH, AlH, Be, Mg, O, S, PH, NH (12); replacement of CH at C-3 in bicyclo[3.2.1]octa-3,6-dien-2-yl anion with PH, S, NH, O (13); and replacement at C-2 and C-3 with N and O (14). Stabilization energies (SE) are evaluated using density functional theory and homodesmotic equations at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) level for series 12-14. Stabilization energies are compared with diamagnetic susceptibility exaltations, Lambda, CSGT-B3LYP/6-31G(d)//B3LYP/6-31G(d), and nucleus-independent chemical shifts (NICS), GIAO-B3LYP/6-311+G(2d,p)//B3LYP/6-31G(d). Analysis of frontier orbitals and geometries, B3LYP/6-31G(d)//B3LYP/6-31G(d), and proton affinities of 2-azabicyclo[3.2.1]octa-3,6-diene, pyrrole, and related model systems, B3LYP/6-311+G(2d,2p)//B3LYP/6-31G(d), provide complementary evidence supporting the division of the substrates evaluated into antihomoaromatic (12, X = BH, AlH, and Be), nonhomoaromatic (12, X = O, S, NH, PH), and homoaromatic (13, X = S, PH, NH, O and 14 X = ON), with 12 (X = Mg) appearing as transitional between anti- and nonhomoaromatic.

Bridged Bicyclo Compounds↗
PubMed2005

Nanolithography based on the formation and manipulation of nanometer-size organic liquid menisci.

Nanometer-size menisci of organic liquids such as octane and 1-octene have been formed and used to confine chemical reactions. The application of a bias voltage between a conductive scanning probe tip separated a few nanometers from a silicon surface allows the field-induced formation of nanometer-size liquid menisci that can subsequently be used to fabricate nanometer-size structures. We report the fabrication of sub-10-nm nanostructures in 0.1 ms. Growth kinetics studies reveal that the nanostructure composition and its formation mechanism are organic-solvent-dependent. Both voltage polarities can be used to grow nanostructures, although the growth rate is significantly higher for positively biased samples. These experiments allow us to produce in the same sample two chemically different nanostructures that are easily addressed and positioned and have sub-10-nm features.

Alkenes↗
PubMed2000

Investigating the specificity of regulators of degradation of hydrocarbons and hydrocarbon-based compounds using structure-activity relationships.

Microbial biosensors which have genes for bioluminescence coupled to genes that control hydrocarbon degradation pathways can be used as reporters on the specificity of regulation of those pathways. Structure-activity relationships can be used to discover what governs that specificity, and can also be used to separate compounds into different groups depending on mode of action. Published data for four different bioluminescent biosensors, reporting on toluene (two separate biosensors), isopropylbenzene, and octane, were analyzed to develop structure-activity relationships between biological response and physical/chemical properties. Good QSARs (quantitative structure-activity relationships) were developed for three out of the four biosensors, with between 88 and 100 per cent of the variance explained. Parameters found to be important in controlling regulator specificity were hydrophobicity, lowest unoccupied molecular orbital energies, and molar volume. For one of the biosensors, it was possible to show that the biological response to chemicals tested fell into three separate classes (non-hydrocarbons, aliphatic hydrocarbons, and aromatic hydrocarbons). A statistically significant QSAR based on hydrophobicity was developed for the fourth biosensor, but was poor in comparison to the other three (44 per cent variance explained).

Bacterial Proteins↗
PubMed1999

[O44--a solvent for silicone oil adhesions on intraocular lenses].

AIM: To examine the efficiency of O44, a partial fluorinated octane, as a solvent for silicone oil adhesions on intraocular lenses. MATERIALS AND METHODS: After placing silicone- and PMMA-lenses in silicone oil, the adhesions were treated with O44. The extent of silicone oil adhesions and the effectiveness of O44 were studied by gross microscopy by scanning electrone microscopy (SEM) and combined energy dispersive spectrometry (EDX). Furthermore an explanted silicone lens with oil adhesions was treated with O44 and examined. To simulate the effect of adhesion proteins PMMA- and silicone lenses were placed in silicone oil and human plasma. RESULTS: With EDX it was possible to prove that O44 is able to remove silicone oil adhesions from PMMA-lenses. The removal from an explanted silicone lens by O44 could be demonstrated by light microscopy. Silicone oil adhesions on intraocular lenses (IOL's) in vitro showed a different oil coverage than the IOL in vivo. Silicone lenses in vitro were often covered by a homogenous oil film and therefore the demonstration of the silicone adhesions and of the efficacy of O44 was difficult. The adhesions of IOL's placed additional in human plasma did not show any differences. CONCLUSIONS: O44 may be a successful intraoperative tool to remove silicone oil adhesions avoiding explantation of silicone oil contaminated IOL's. Silicone oil adhesions in vivo seem to be influenced by adhesive proteins.

Efficiency↗
PubMed2000

Peptide interfacial adsorption is kinetically limited by the thermodynamic stability of self association.

We present a study of the adsorption of two peptides at the octane-water interface. The first peptide, Lac21, exists in mixed monomer-tetramer equilibrium in bulk solution with an appreciable monomer concentration. The second peptide, Lac28, exists as a tetramer in solution, with minimal exposed hydrophobic surface. A kinetic limitation to interfacial adsorption exists for Lac28 at moderate to high surface coverage that is not observed for Lac21. We estimate the potential energy barrier for Lac28 adsorption to be 42 kJ/mol and show that this is comparable to the expected free energy barrier for tetramer dissociation. This finding suggests that, at moderate to high surface coverage, adsorption is kinetically limited by the availability of interfacially active monomeric "domains" in the subinterfacial region. We also show how the commonly used empirical equation for protein adsorption dynamics can be used to estimate the potential energy barrier for adsorption. Such an approach is shown to be consistent with a formal description of diffusion-adsorption, provided a large potential energy barrier exists. This work demonstrates that the dynamics of interfacial adsorption depend on protein thermodynamic stability, and hence structure, in a quantifiable way.

Adsorption↗
PubMedDate not supplied

Exposures to benzene and other volatile compounds from active and passive smoking.

Personal exposures and breath concentrations of approximately 20 volatile organics were measured for 200 smokers and 322 nonsmokers in New Jersey and California. Smokers displayed significantly elevated breath levels of benzene, styrene, ethylbenzene, m + p-xylene, o-xylene, and octane. Significant increases in breath concentration with number of cigarettes smoked were noted for the first four aromatic compounds. Based on direct measurements of benzene in mainstream cigarette smoke, it is calculated that a typical smoker inhales 2 mg benzene daily, compared to 0.2 mg/day for the nonsmoker. Thus, cigarette smoking may be the most important source of exposure to benzene for about 50 million citizens of the United States. Passive smokers exposed at work had significantly elevated levels of aromatics in their breath. Indoor air levels in homes with smokers were significantly greater than in nonsmoking homes during fall and winter but not during spring and summer. The average annual increase in homes with smokers was 3.6 microgram/m3 for benzene and 0.5 microgram/m3 for styrene--an approximate 50% relative increase in each case. Thus, exposure to benzene and styrene may be increased for the approximately 60% of children and other nonsmokers living in homes with smokers.

Benzene Derivatives↗
PubMed2006

Migration and sensory properties of plastics-based nets used as food-contacting materials under ambient and high temperature heating conditions.

Overall migration from a wide range of commercial plastics-based netting materials destined to be used as either meat or vegetable packaging materials into the fatty food simulant isooctane or the aqueous simulant distilled water, respectively, was studied. In addition, sensory tests of representative netting materials were carried out in bottled water in order to investigate possible development of off-odour/taste and discoloration in this food simulant as a result of migration from the netting material. Sensory tests were supplemented by determination of the volatile compounds' profile in table water exposed to the netting materials using SPME-GC/MS. Test conditions for packaging material/food simulant contact and method of overall migration analysis were according to European Union Directives 90/128 (EEC, 1990) and 2002/72 (EEC, 2002). The results showed that for both PET and polyethylene-based netting materials, overall migration values into distilled water ranged between 11.5 and 48.5 mg l(-1), well below the upper limit (60 mg l(-1)) for overall migration values from plastics-packaging materials set by the European Union. The overall migration values from netting materials into isooctane ranged between 38.0 and 624.0 mg l(-1), both below and above the European Union upper limit for migration. Sensory tests involving contact of representative samples with table water under refluxing (100 degrees C/4 h) conditions showed a number of the netting materials produced both off-odour and/or taste as well as discoloration of the food simulant rendering such materials unfit for the packaging of foodstuffs in applications involving heating at elevated temperatures. GC/MS analysis showed the presence of numerous volatile compounds being produced after netting materials/water contact under refluxing conditions. Although it is extremely difficult to establish a clear correlation between sensory off-odour development and GC/MS volatile compounds' profile, it may be postulated that plastics oxidation products such as hexanal, heptanal, octanal and 2,6 di-tert-butylquinone may contribute to off-odour development using commercially bottled table water as a food simulant. Likewise, compounds such as carbon disulfide, [1,1'-biphenyl]-2-ol and propanoic acid, 2 methyl 1-(1,1-dimethyl)-2-methyl-1,3-propanediyl ester probably originating from cotton and rubber components of netting materials may also contribute to off-odour/taste development.

Color↗