A study of acid/base treatments of polypyrrole films using 13C n.m.r. spectroscopy

Electrodeposited polypyrrole films prepared with paratoluenesulfonate (pTS), dodecylsulfate (DDS) and perchlorate anions were treated with acidic and basic solutions, and their structure was investigated by 13C solid state n.m.r. spectroscopy. This technique has confirmed that pTS is completely removed from the film in both acidic and basic solutions whilst DDS is only partially removed and tends to decompose upon treatment with H2SO4. The appearance of shoulders at 143 ppm upon treatment with 0.5 M base indicates formation of a quinoid pyrrole structure. Substitution on the β-carbon by OH cannot be confirmed from the present spectra. Stronger base causes a more dramatic change in the polypyrrole backbone with an obvious increase in the electron density on the β-carbons, consistent with the reduction of the carbon backbone. There is no indication of quinoid units in this case. Acid treatments result in considerable broadening of the main 127 ppm polypyrrole peak.

Mesityltellurenyl cations stabilized by triphenylpnictogens [MesTe(EPh₃)] + (E = P, As, Sb)

The homoleptic 1:1 Lewis pair (LP) complex [MesTe(TeMes₂)]O₃SCF₃ (1) featuring the cation [MesTe(TeMes₂)]+ (1a) was obtained by the reaction of Mes₂Te with HO₃SCF₃. The reaction of 1 with Ph₃E (E = P, As, Sb, Bi) proceeded with substitution of Mes₂Te and provided the heteroleptic 1:1 LP complexes [MesTe(EPh₃)]O₃SCF₃ (2, E = P; 3, E = As) and [MesTe(SbPh₃)][Ph₂Sb(O₃SCF₃)₂] (4) featuring the cations [MesTe(EPh₃)]+ (2a, E = P; 3a, E = As; 4a, E = Sb) and the anion [Ph₂Sb(O₃SCF₃)₂]− (4b). In the reaction with Ph₃Bi, the crude product contained the cation [MesTe(BiPh₃)]+ (5a) and the anion [Ph₂Bi(O₃SCF₃)₂]− (5b); however, the heteroleptic 1:1 LP complex [MesTe(BiPh₃)][Ph₂Bi(O₃SCF₃)₂] (5) could not be isolated because of its limited stability. Instead, fractional crystallization furnished a large amount of Ph₂BiO₃SCF₃ (6), which was also obtained by the reaction of Ph₃Bi with HO₃SCF₃. The formation of the anions 4b and 5b involves a phenyl group migration from Ph₃E (E = Sb, Bi) to the MesTe+ cation and afforded MesTePh as the byproduct, which was identified in the mother liquor. The heteroleptic 1:1 LP complexes 2–4 were also obtained by the one-pot reaction of Mes₂Te, Ph₃E (E = P, As, Sb) and HO₃SCF₃. Compounds 1–4 and 6 were investigated by single-crystal X-ray diffraction. The molecular structures of 1a–4a were used for density functional theory calculations at the B3PW91/TZ level of theory and studied using natural bond order (NBO) analyses as well as real-space bonding descriptors derived from an atoms-in-molecules (AIM) analysis of the theoretically obtained electron density. Additionally, the electron localizability indicator (ELI-D) and the delocalization index are derived from the corresponding pair density.

Transmission electron microscopy characterization of the bake-hardening behavior of transformation-induced plasticity and dual-phase steels

The effect of prestraining (PS) and bake hardening (BH) on the microstructures and mechanical properties has been studied in transformation-induced plasticity (TRIP) and dual-phase (DP) steels after intercritical annealing. The DP steel showed an increase in the yield strength and the appearance of the upper and lower yield points after a single BH treatment as compared with the as-received condition, whereas the mechanical properties of the TRIP steel remained unchanged. This difference appears to be because of the formation of plastic deformation zones with high dislocation density around the “as-quenched” martensite in the DP steel, which allowed carbon to pin these dislocations, which, in turn, increased the yield strength. It was found for both steels that the BH behavior depends on the dislocation rearrangement in ferrite with the formation of cell, microbands, and shear band structures after PS. The strain-induced transformation of retained austenite to martensite in the TRIP steel contributes to the formation of a complex dislocation structure.

Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography

We report on the characterization of grain boundary (GB) segregation in an Fe-28Mn-0.3C (wt.%) twinning-induced plasticity (TWIP) steel. After recrystallization of this steel for 24 h at 700 °C, ∼50% general grain boundaries (GBs) and ∼35% Σ3 annealing twin boundaries were observed (others were high-order Σ and low-angle GBs). The segregation of B, C and P and traces of Si and Cu were detected at the general GB by atom probe tomography (APT) and quantified using ladder diagrams. In the case of the Σ3 coherent annealing twin, it was necessary to first locate the position of the boundary by density analysis of the atom probe data, then small amounts of B, Si and P segregation and, surprisingly, depletion of C were detected. The concentration of Mn was constant across the interface for both boundary types. The depletion of C at the annealing twin is explained by a local change in the stacking sequence at the boundary, creating a local hexagonal close-packed structure with low C solubility. This finding raises the question of whether segregation/depletion also occurs at Σ3 deformation twin boundaries in high-Mn TWIP steels. Consequently, a previously published APT dataset of the Fe-22Mn-0.6C alloy system, containing a high density of deformation twins due to 30% tensile deformation at room temperature, was reinvestigated using the same analysis routine as for the annealing twin. Although crystallographically identical to the annealing twin, no evidence of segregation or depletion was found at the deformation twins, owing to the lack of mobility of solutes during twin formation at room temperature.

Experimental evolution reveals that population density does not affect moth signalling behaviour and antennal morphology

Population density can play a vital role in determining investment in reproductive behaviours and morphologies of invertebrates. Males reared in high-density environments, where competition is high but difficulties in locating mates are low, may invest more in reproductive structures associated with sperm competition such as testes, at the expense of those traits associated with mate location, such as antennae. In species where females advertise for mates, such as most moths, a high-density environment may also lead to a reduction in pheromonal signalling (calling) length and frequency as a result of high mate abundance. While such responses have been shown at the phenotypically plastic level in moths, heritable evolutionary adaptations have seldom been tested, and studies of how population density influences pheromone signalling strategies are scarce. Here we use behavioural assays and scanning electron microscopic measurements to test whether larval population density influences, at the genetic level, the ability of males to locate females and male investment into antennal morphology, in addition to its effect on the frequency and duration of female calling. We used two replicated populations of the Indian meal moth Plodia interpunctella that had experimentally evolved under high or low population densities for 35 generations. We found no significant divergence in antennal morphology or mate acquisition behaviours between the two density populations. These findings suggest that although population density has the ability to create plastic changes in both morphological and behavioural traits, this factor alone is unlikely to be causing evolutionary change in male and female signalling in this species.