Eiffel assertions and the external structure of classes and objects

The “external structure” in an object oriented system refers here to the  graphs of objects and classes. The class structure graph or class model is derived from the object structure graph or object model, and in this operation structural information is lost, or never made explicit. Although object oriented programming languages capture the class model as declarations,  contradictory assumptions about object model properties may be made introducing faults into the design. Consistent assumptions about the object model can be specified in the code using assertions such as Eiffel’s  invariants, preconditions and postconditions. Three examples specifying the external structure are considered.

Inverse opal structure of SnO2 and SnO2 : Zn for gas sensing

In the present work, we propose a low cost synthetic sol-gel route that allows to produce high quality oxide nanostructures with inverse opal architecture which, transferred on alumina substrates provided with Pt interdigitated contacts and heater, are tested as gas sensing devices. An opal template of sintered monodisperse polystyrene spheres was filled with alcoholic solutions of metal oxide precursors and transferred on the alumina substrate. The polystyrene template was removed by thermal treatment, leading to the simultaneous sintering of the oxide nanoparticles. Beside SnO₂, a binary oxide well known for gas sensing application, a Zn containing ternary solid solution (SnO₂:Zn, with Zn 10% molar content) was taken into account for sensor preparation. The obtained high quality macro and meso-porous structures, characterized by different techniques, were tested for pollutant (CO, NO₂) and interfering (methanol) gases, showing that very good detection can be reached through the increase of surface area offered by the inverse opal structure and the tailoring of the chemical composition. The electrical characterization performed on the tin dioxide based sensors shows an enhancement of the relative response towards NO₂ at low temperatures in comparison with conventional SnO₂ sensors obtained with sputtering technique. The addition of Zn increases the separation between the operating temperatures for reducing and oxidizing gases and results in a further enhancement of the selectivity to NO₂ detection.

Female–female aggression : structure of interaction and outcome in loggerhead sea turtles

Aggressive behaviour between females of the same species is not widely documented, particularly in marine vertebrates. During a 3 yr in-water survey at the temperate loggerhead sea turtle Caretta caretta breeding area of Zakynthos, Greece, female–female interactions comprised 4% of all female loggerhead sighting events (n = 60 out of 1449 events). Male–female interactions comprised an additional 4% of sighting events, while 92% were of solitary females. The structure of interactions was analysed for 58 of these sighting events, each lasting an average of 3.4 min (SD ± 1) and comprising a total of 3.1 h observation time. We found that interactions involved ritualized escalation in behaviour from passive threat displays (e.g. head–tail circling) to aggressive combat (e.g. sparring). We suggest that circling individuals evaluate opponent size, sparring individuals test opponent strength, and that the positioning of the prehensile tail signals motivational intent to either escalate or abort. The presence of intruder females triggered a passive response in 100% of events involving basking and swimming turtles (n = 19); although residents resting on the seabed only responded on 69% of occasions (n = 27), their response was almost 4 times more likely to escalate to one of aggression. Our results suggest that certain sites may be preferentially sought after and defended by sea turtles.

Perceptive variation of carboxylate ligand and probing the influence of substitution pattern on the structure of mono- and di-butylstannoxane complexes

By reacting 2- and 3-aminobenzoic acids (HL1 and HL2, respectively), as well as 2-, 3- and 4-((E)-2-[4-(dimethylamino)phenyl]diazenyl)benzoic acids (HL3, HL4 and HL5, in this order) with a n-butyltin(IV) source [ n BuSn(O)OH or n Bu2SnO], the drum-type butylstannoxane complexes of general composition [ n Bu6Sn6O6(L n )6] [L n =L1 (1), L2 (2) and L3 (3)] and the ladder-type compounds [ n Bu8Sn4O2(L n )4] [L n =L3 (5), L4 (6) and L5 (7)] were obtained and fully characterized. By reacting 1 with 2-((E)-[4-(dimethylamino)benzylidene]amino)benzoic acid (HL6), a co-crystal (4) was achieved which comprises the metal complex aggregate found in 1 and the neutral HL6 molecule. The solution properties of the compounds were assessed from 1H and 13C NMR studies and, for the metal complexes, also from 119Sn NMR. The molecular structures of 1, 2, 4-7 were confirmed by single-crystal X-ray diffraction. Compounds 1-3 and the complex moiety of 4 display hexameric Sn6O6 clusters with drum-like structures, but 5-7 reveal Sn4O2 cores with ladder-type structural motifs. Besides the observed relationship between the ligand N-functional group and obtained (drum- or ladder-type) assemblies, the relative position of the carboxylate group in the ligand itself influences its coplanarity.

Double layer structure of ionic liquids at the Au(111) electrode interface : an atomic force microscopy investigation

The double layer structure of two ionic liquids (ILs), 1-butyl-1- methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py ₁,₄]FAP) and 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([EMIm]FAP) at the polarized Au(111) electrode interface is probed using Atomic Force Microscopy force measurements. The force-separation profiles suggest a multilayered morphology is present at the electrified Au(111)-IL interface, with more near surface layers detected at higher potentials. At the (slightly negative) open circuit potential, multiple ion layers are present, and the innermost layer, in contact with the Au(111) surface, is enriched in the cation due to electrostatic adsorption. Upon applying negative electrode potentials (-1.0 V, -2.0 V), stronger IL near surface structure is detected: both the number of ion layers and the force required to rupture these layers increases. Positive electrode potentials (+1.0 V, +2.0 V) also enhance IL near surface structure, but not as much as negative potentials, because surface-adsorbed anions are less effective at templating structure in subsequent layers than cations. This interfacial structure is not consistent with a double layer in the Stern-Gouy-Chapman sense, as there is no diffuse layer. The structure is consistent with a capicitative double-layer model, with a very small separation distance between the planes of charge.

Growth and structure of prismatic boron nitride nanorods

Prismatic boron nitride nanorods have been grown on single crystal silicon substrates by mechanical ball-milling followed by annealing at 1300 °C. Growth takes place by rapid surface diffusion of BN molecules, and follows heterogeneous nucleation at catalytic particles of an Fe/Si alloy. Lattice imaging transmission electron microscopy studies reveal a central axial row of rather small truncated pyramidal nanovoids on each nanorod, surrounded by three basal planar BN domains which, with successive deposition of epitaxial layers adapt to the void geometry by crystallographic faceting. The bulk strain in the nanorods is taken up by the presence of what appear to be simple nanostacking faults in the external, near-surface domains which, like the nanovoids are regularly repetitive along the nanorod length. Growth terminates with a clear cuneiform tip for each nanorod. Lateral nanorod dimensions are essentially determined by the size of the catalytic particle, which remains as a foundation essentially responsible for base growth. Growth, structure, and dominating facets are shown to be consistent with a system which seeks lowest bulk and surface energies according to the well-known thermodynamics of the capillarity of solids.

Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e− Fc+ (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc+ as the hexafluorophosphate (PF6−) or tetrafluoroborate (BF4−) salts and their mixtures in three ionic liquids (ILs) (1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc+ differ significantly and are a function of the Fc and Fc+ concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media. Thus, the Faradaic currents associated with the oxidation of Fc (Fc0/+) and reduction of FcPF6 or FcBF4 (Fc+/0) when both Fc and Fc+ are simultaneously present in the ILs differ from values obtained when individual Fc and Fc+ solutions are used. The voltammetry for both the Fc0/+ and Fc+/0 processes exhibited near-Nernstian behavior at a glassy carbon macrodisk electrode and a platinum microdisk electrode, when each process was studied individually in the ILs. As expected, the reversible formal potentials (E°′) and diffusion coefficients (D) at 23 ± 1 °C were independent of the electrode material and concentration. However, when Fc and FcPF6 or FcBF4 were both present, alterations to the mass transport process occurred and apparent D values calculated for Fc and Fc+ were found to be about 25−39% and 32−42% larger, respectively, than those determined from individual solutions. The apparent value of the double layer capacitance determined by FT-ac voltammetry from individual and mixed Fc and Fc+ conditions at the GC electrode was also a function of concentration. Double layer capacitance values increased significantly with the concentration of Fc and FcPF6 or FcBF4 when species were studied individually or simultaneously, but had a larger magnitude under conditions where both species were present. Variation in the structure of the ILs and hence mobilities of the ionic species, when Fc and FcPF6 or FcBF4 are simultaneously present, is considered to be the origin of the nonadditivity of the Faradaic currents and variation in capacitance.

Solvent induced changes in the conformational state of β-lactoglobulin and the influence of protic ionic liquids

The protic ionic liquids (pILs), triethylammonium acetate, triethylammonium trifluoroacetate, triethylammonium mesylate and trimethylammonium sulfate were used to induce various native and non-native conformational states of the protein β-lactoglobulin (βLG). Changes in the secondary structure of βLG were observed on moving from a high water content to a high pIL content. We examined the stability of various pIL induced states via thermal unfolding and refolding, where it was found that at a given pIL concentration a highly stable non-native conformation was formed. The βLG non-native conformation was characterized by a high α-helical content. Additionally, pIL conditions that promoted amyloid fibril formation were identified and characterized by CD, a Thioflavin T binding assay and transmission electron microscopy (TEM). This work highlights the use of pILs as solvents in the study of protein folding using βLG as a model system.