Ammonium recognition by 18-crown-6 in different solutions and at an aqueous interface: a simulation study.

The complexation of alkylammonium RNH3(+) cations by 18-crown-6 (18C6) is studied by molecular dynamics (MD) and potential of mean force (PMF) simulations in different solvents (methanol, chloroform, 90:10 chloroform/methanol mixture, water) and at the chloroform/water interface. The free energies of association ΔGass, obtained with different charge models of 18C6, are compared for PrNH3(+) and K(+) cations yielding, with suitable electrostatic models, a preference for K(+) in the different monophasic solutions, as well as in the gas phase. Furthermore, for a given cation, ΔGass is markedly solvent dependent and decreases in magnitude in the order chloroform ≫ mixture > methanol > water, that is, with the (de)solvation energy of the cation and with the extent of pairing with the counterion (here, picrate, Pic(-)). Despite their macroscopic intermiscibilities at all proportions, chloroform and methanol are found to form, at the microscopic level, an inhomogeneous liquid that displays dual solvation properties toward its solutes. As a result, in the monophasic 90:10 mixture that contains mainly chloroform, the ΔGass energies for PrNH3(+) or K(+) complexation are closer to those in methanol than to those in chloroform. On the other hand, chloroform and water form a biphasic mixture and delineate an interface onto which 18C6 and the tBuNH3(+) and Pic(-) ions, as well as their complex, are found to adsorb, a feature also supported by the different free energy profiles for interface crossing. Interestingly, the complexation energy of tBuNH3(+) is found to be stronger at the interface than in pure water, demonstrating the crucial role of complexation by 18C6 at the interface to promote the cation transfer to the organic phase.

Liquid-liquid extraction of uranyl by TBP: the TBP and ions models and related interfacial features revisited by MD and PMF simulations.

We report a molecular dynamics (MD) study of biphasic systems involved in the liquid-liquid extraction of uranyl nitrate by tri-n-butylphosphate (TBP) to hexane, from "pH neutral" or acidic (3 M nitric acid) aqueous solutions, to assess the model dependence of the surface activity and partitioning of TBP alone, of its UO2(NO3)2(TBP)2 complex, and of UO2(NO3)2 or UO2(2+) uncomplexed. For this purpose, we first compare several electrostatic representations of TBP with regards to its polarity and conformational properties, its interactions with H2O, HNO3, and UO2(NO3)2 species, its relative free energies of solvation in water or oil environments, the properties of the pure TBP liquid and of the pure-TBP/water interface. The free energies of transfer of TBP, UO2(NO3)2, UO2(2+), and the UO2(NO3)2(TBP)2 complex across the water/oil interface are then investigated by potential of mean force (PMF) calculations, comparing different TBP models and two charge models of uranyl nitrate. Describing uranyl and nitrate ions with integer charges (+2 and -1, respectively) is shown to exaggerate the hydrophilicity and surface activity of the UO2(NO3)2(TBP)2 complex. With more appropriate ESP charges, mimicking charge transfer and polarization effects in the UO2(NO3)2 moiety or in the whole complex, the latter is no more surface active. This feature is confirmed by MD, PMF, and mixing-demixing simulations with or without polarization. Furthermore, with ESP charges, pulling the UO2(NO3)2 species to the TBP phase affords the formation of UO2(NO3)2(TBP)2 at the interface, followed by its energetically favorable extraction. The neutral complexes should therefore not accumulate at the interface during the extraction process, but diffuse to the oil phase. A similar feature is found for an UO2(NO3)2(Amide)2 neutral complex with fatty amide extracting ligands, calling for further simulations and experimental studies (e.g., time evolution of the nonlinear spectroscopic signature and of surface tension) on the interfacial landscape upon ion extraction.

Liquid-liquid extraction of uranyl by an amide ligand: interfacial features studied by MD and PMF simulations.

We report a molecular dynamics study of biphasic systems involved in the liquid-liquid extraction of uranyl nitrate by a monoamide ligand (L = N,N-di(2-ethylhexyl)isobutyramide, DEHiBA) to hexane, from pH neutral or acidic (3 M nitric acid) aqueous solutions. We first describe the neat interfaces simulated with three electrostatic models, one of which including atomic polarizabilities. The free energy profiles for crossing the water/hexane interface by L or its UO2(NO3)2L2 complex are then investigated by PMF (potential of mean force) calculations. They indicate that the free ligand and its complex are surface active. With the polarizable force field, however, the complexes have a lower affinity for the interface than without polarization. When DEHiBA gets more concentrated and in acidic conditions, their surface activity diminishes. Surface activity of UO2(NO3)2L2 complexes is further demonstrated by demixing simulations of randomly mixed DEHiBA, hexane, and neutral or acidic water. Furthermore, demixing of randomly mixed solvents, L molecules, UO2(NO3)2 salts, and nitric acid shows in some cases complexation of L to form UO2(NO3)2L2 and UO2(NO3)2L complexes that adsorb at the aqueous interfaces. These features suggest that uranyl complexation by amide ligands occurs "right at the interface", displaying marked analogies with the liquid-liquid extraction of uranyl by TBP (tri-n-butyl phosphate). Regarding the positive effect of nitric acid on extraction, the simulations point to several facets involving enhanced ion pairing of uranyl nitrate, decreased affinity of the complex for the interface, and finally, stabilization of the complex in the organic phase.

Oil-soluble and water-soluble BTPhens and their europium complexes in octanol/water solutions: interface crossing studied by MD and PMF simulations.

Bistriazinyl-phenantroline "BTPhen" ligands L display the remarkable feature to complex trivalent lanthanide and actinide ions, with a marked selectivity for the latter. We report on molecular dynamics studies of tetrasubstituted X(4)BTPhens: L(4+) (X = (+)Et(3)NCH(2)-), L(4-) (X = (-)SO(3)Ph-), and L(0) (X = CyMe(4)) and their complexes with Eu(III) in binary octanol/water solutions. Changes in free energies upon interface crossing are also calculated for typical solutes by potential of mean force PMF simulations. The ligands and their complexes partition, as expected, to either the aqueous or the oil phase, depending on the "solubilizing" group X. Furthermore, most of them are found to be surface active. The water-soluble L(4+) and L(4-) ligands and their (L)Eu(NO(3))(3) complexes adsorb at the aqueous side of the interface, more with L(4-) than with L(4+). The oil soluble ligand L(0) is not surface active in its endo-endo form but adsorbs on the oil side of the interface in its most polar endo-exo form, as well as in its protonated L(0)H(+) and complexed (L(0))Eu(NO(3))(3) states. Furthermore, comparing PMFs of the Eu(III) complexes with and without nitric acid shows that acidifying the aqueous phase has different effects, depending on the ligand charge. In particular, acid promotes the Eu(III) extraction by L(0) via the (L(0))(2)Eu(NO(3))(2+) complex, as observed experimentally. Overall, the results point to the importance of interfacial adsorption for the liquid-liquid extraction of trivalent lanthanide and actinide cations by BTPhens and analogues.

Basicity, complexation ability and interfacial behavior of BTBPs: a simulation study.

BTBPs represent an important class of tetradentate heterocyclic ligands with N-donor binding sites that have been recently developed to separate trivalent actinides from lanthanides. We first investigate by QM calculations the conformational properties, basicity and complexation energies with Eu(NO(3))(3), comparing BTBP derivatives with alkyl substituents on the pyridinyl or triazinyl moieties to their conformationally cis-locked BTPhen analogues. The latter, preorganized for protonation and complexation, are found to be more basic and to afford more stable complexes. We next explore the interfacial behavior of CyMe(4)BTBP in its neutral versus protonated states and of 1:1 Eu(NO(3))(3)(CyMe(4)BTBP) complexes at the aqueous interface with an octanol-hexane mixture. The neutral BTBP ligand displays no visible surface activity, whereas protonated and complexed ligands are surface active. Taken together, the QM and MD results suggest that Eu(III) extraction by BTBPs occurs at the interface, via the protonated form of the ligand in acidic conditions, explaining why the extraction kinetics is slow and why BTPhen ligands are more efficient than BTBPs.

BTP-based ligands and their complexes with Eu(3+) at "oil"/water interfaces. A molecular dynamics study.

Heterocyclic N-donor ligands based on the bistriazinylpyridine (BTPs) skeleton have been recently developed to separate trivalent actinides from lanthanides by liquid-liquid extraction from nuclear solutions. In this paper, we report molecular dynamics investigations on BTPs in water-"oil" biphasic systems (oil = hexane + octanol vs. hexane vs. nitrobenzene vs. chloroform) and compare different BTP derivatives, their neutral vs. protonated forms, and their 1 : 3 complexes with Eu((III)). Neutral BTPs are found to be weakly surface active and to display multiple orientations at the interface, depending on time and on their lateral and para substituents. This contrasts with their protonated forms that strongly adsorb at interfaces with neutral or acidic water. Remarkably, the protonated cyMe(4)-BTPH(+) and, to a lesser extent, (i)PrBTPH(+) ligands adopts at the interface an "inversed orientation", where NH(+) points towards oil, instead of water. The [Eu(BTP)(3)](3+) complexes are also found to be highly surface active: in spite of Eu((III)) shielding by the three ligands, these complexes remain strongly attracted by water at the aqueous side of the interface. Taken together, the MD results suggest that ion complexation by BTPs occurs right at the interface, from the protonated BTPH(+) forms. They may explain why extraction is improved upon increase of the aqueous phase acidity, though with slow kinetics. They also open perspectives for designing new derivatives for efficient separation of trivalent actinides from lanthanides.

Influence of autoclave sterilization on the surface parameters and mechanical properties of six orthodontic wires.

Orthodontic wires are frequently packaged in individual sealed bags in order to avoid cross-contamination. The instructions on the wrapper generally advise autoclave sterilization of the package and its contents if additional protection is desired. However, sterilization can modify the surface parameters and the mechanical properties of many types of material. The aim of this research was to determine the influence of one of the most widely used sterilization processes, autoclaving (18 minutes at 134 degrees C, as recommended by the French Ministry of Health), on the surface parameters and mechanical properties of six wires currently used in orthodontics (one stainless steel alloy: Tru-Chrome RMO; two nickel-titanium shape memory alloys: Neo Sentalloy and Neo Sentalloy with Ionguard GAC; and three titanium-molybdenum alloys: TMA(R) and Low Friction TMA Ormco and Resolve GAC). The alloys were analysed on receipt and after sterilization, using surface structure observation techniques, including optical, scanning electron and atomic force microscopy and profilometry. The mechanical properties were assessed by three-point bending tests. The results showed that autoclave sterilization had no adverse effects on the surface parameters or on the selected mechanical properties. This supports the possibility for practitioners to systematically sterilize wires before placing them in the oral environment.

In vitro streptococcal adherence on prosthetic and implant materials. Interactions with physicochemical surface properties.

The aim of this study was to evaluate streptococcal adherence to eight currently used prosthetic and implant materials, and enamel samples, after a salivary coating and to investigate the influence of substrata surface free energy (SFE) and its polar and non-polar components, as well as bacterial surface characteristics, on bacterial adherence. Our results indicate a moderate hydrophobic character of saliva-coated surfaces and a pronounced basic character of the polar component of SFE values, except for one substrata. The lowest colonization was observed with enamel samples and the lowest values of adherent bacteria on the different substrata were observed with the hydrophilic bacterial strain. Both the nature of the substrata and the nature of the bacterial strains could have an effect on the extent of bacterial adhesion. When the interrelationship between the number of adherent bacteria and the surface properties of bacteria and substrata were analysed, bacterial adherence correlated with the non-polar component of substrata SFE (r = 0.8, P = 0.02) and with the adhesion to the solvents (r = 0.8, P < 0.0001). These results are consistent with the thermodynamic theory and underline the importance of acid-base characteristics of the cell surface when one is studying bacterial adherence on dental casting alloys and implant materials.

Effect of hydrophobicity on in vitro streptococcal adhesion to dental alloys.

Non-specific interactions such as electrostatic interactions, and surface free energy are of importance in bacterial adhesion to dental surfaces as they determine whether or not bacteria are attracted to the surface. The relationship between adherence of Streptococcus mitis, S. mutans, S. oralis and S. sanguinis on precious and non-precious dental alloys, and the bacterial and alloy surface hydrophobicities (a measure of the surface free energy) was studied. The number of adhering bacteria was determined by fluorescence microscopy counts. The hydrophobicity of the bacteria and alloy surfaces were evaluated by adhesion to hexadecane and water contact angles, respectively. Our results showed that (i) the surfaces of the tested alloys were hydrophobic, (ii) S. sanguinis, S. mutans and S. oralis were hydrophobic, and (iii) S. mitis was hydrophilic. S. oralis, the more hydrophobic strain, demonstrated the highest adherence on the tested materials, whereas S. mitis adhered least on the hydrophobic surfaces. For the tested alloys, bacterial adherence was highest for the high gold content alloy, and lowest for the non-precious alloy. Our results showed that for the tested bacterial strains, there was a significant correlation between bacterial adhesion and substratum hydrophobicity: hydrophobic metal surfaces favor adhesion of hydrophobic bacteria.

In vitro evaluation of the antibacterial effects of intracanal micro plasma system treatment.

Forty freshly extracted single-rooted teeth were prepared to a size 25 master apical file, autoclaved, and inoculated with a known quantity of Actinomyces naeslundii. The teeth were divided into four groups (n = 10), including an untreated control group. The three treatment groups were exposed to Micro Plasma System (MPS), 0.5% NaOCl and 0.5% NaOCl + MPS respectively. The content of each root canal was absorbed by sterile paper points, diluted in 2 ml Schaedler Broth Medium, and incubated on blood agar. The number of CFU was determined. Data analysis, using an analysis of variance and Scheffe's test at the 1% level (Statview II software), indicated a significant reduction in CFU count for the three treatment groups compared to the control group. For the three treatment groups, no significant intergroup differences were observed.

rRNA gene restriction patterns as possible taxonomic tools for the genus actinomyces.

Species delineation in the genus Actinomyces remains unclear, particularly regarding the two taxa, A. naeslundii and A. viscosus. The ribotyping patterns of 64 strains of Actinomyces, representing 8 species and comprising different serotypes, were studied as possible taxonomic tools, using an acetyl-aminofluorene (AAF)-labelled E. coli 16S + 23S rRNA probe. Similarities between patterns were assessed using Jaccard's coefficient and clustering achieved using the unweighted pair-group method with average linkage (UPGMA) on a Macintosh II (Apple, Cupertino, USA) computer. The dendrogram obtained from the ribotypes gave results which were in reasonable agreement with many previous reports: A. bovis, A. gerensceriae, A. israelii, A. meyerii, A. odontolyticus and A. pyogenes were found to be distinct species but the two taxa A. naeslundii and A. viscosus remained unclear. Further investigations, using a larger number of A. naeslundii and A. viscosus strains and other endonucleases, need to be carried out to provide more information concerning the relatedness of these two taxa. Nevertheless, these preliminary results suggested that the Actinomyces chromosome contains multiple rRNA operons which may be used as an epidemiological and taxonomical tool.

An investigation into the use of restriction endonuclease analysis for the study of transmission of Actinomyces.

DNA fingerprints of 28 reference strains of Actinomyces, comprising representatives of different species and serotypes, and 19 isolates recovered from 16 periodontal patients was performed. The aim was to determine the potential of the method for detecting strain differences in terms of discriminatory power and to evaluate its usefulness in the typing of Actinomyces strains for eco-epidemiological studies. Among the 17 restriction endonucleases tested, Bst EII, Pvu II and Sma I proved to be the most suitable for the genus Actinomyces restriction digest analysis. Visual comparisons of Bst EII, Pvu II and Sma I digest patterns of chromosomal DNA revealed clear differences within species but also within serotypes of Actinomyces that are otherwise identical. The method offers the qualities for use as an epidemiological tool for identifying sources and tracing routes of transmission of Actinomyces: stability, reproducibility, ease of preparation and interpretation and enough sensitivity for detection of differences between morphologically and serologically similar strains of Actinomyces.

Improved SDS-Page method for protein profiles analysis of actinomyces species.

A simple, rapid SDS-Page method for protein profiles analysis of Actinomyces species was developed. Eighteen strains (12 reference strains and 6 fresh isolates) representing four species were used in this study. Eight detergents were tested for protein extraction. Cell extracts were obtained by shaking the bacteria suspended in a solution containing a detergent and glass beads. After electrophoresis, according to the Laemmli's technique, two protein stain procedure were tested (Coomassie blue and silver stain). Best results were obtained with 0.5% Triton X-100 for 4 h and the silver stain procedure of Oakley. Protein profiles analysis showed that the method is reproducible and distinguishes not only species but sometimes also subspecies.

Rapid isolation of DNA from Actinomyces.

DNA could not be quickly extracted from members of the genus Actinomyces by the usual methods of lysis. Treatment of 7 different actinomyces cells with lysozyme and achromopeptidase, both 5 mg/g wet cells, for 2 h, followed by SDS (0.2%), proteinase K (5 mg/g wet cells) and EDTA (lmM) for 1 h, lysed the cells. The yield obtained in one day was 337 micrograms per 200 mg of bacterial cells. The treatment was also found to work effectively on strains belonging to Veillonella, Staphylococcus, Fusobacterium and Bifidobacterium genera.

[Gas chromatography analysis of volatile monocarboxylic aliphatic acids (C2 to C6) of 15 strains of Veillonella of oral origin]. / Analyse par chromatographie en phase gazeuse des acides aliphatiques monocarboxyliques volatils (C2 à C6) de 15 souches du genre Veillonella d'origine buccale.

A qualitative and quantitative study has been carried out on 15 strains of the Veillonella genus, isolated in the oral cavity. Following two methods of preparation of samples for injection in a chromatograph GL, we have identified among the volatil monocarboxylic aliphatic acids from C2 to C6 the glucose fermentation products of these different strains. With the same methods, we studied in parallel these products from strains A.T.C.C. 10790-17444 (Veillonella parvula) and 17445-17446 and 17447 (Veillonella alcalescens). The results, despite the diversity of origin of all these strains, based on physiological and biochemical characteristics, confirm that volatil monocarboxylic aliphatic acids are characteristic of a genus specificity and not of a species. The presence of acetic acid, proprionic acid and iso-valeric acid was shown