The polymerization of aniline intercalated into montmorillonite clay was monitored by in
situ UV−vis−NIR and resonance Raman spectroscopies and in situ small-angle X-ray scattering. In the
initial stages of the polymerization, it is observed the PANI−ES polaronic band at 750 nm in the UV−vis−NIR spectrum and also the characteristic PANI-ES resonance Raman spectrum (excited at 632.8
nm), which indicate that the head-to-tail coupling reactions between anilinium radical cations are
occurring. Nevertheless, the resonance Raman spectrum excited at 488.0 nm presents bands at 1211,
1370, 1455, and 1608 cm-1, assigned to the benzidine dication species, which suggests that tail-to-tail
coupling reactions are also occurring. In the final stages of polymerization, the presence of electronic
absorption bands at 670 and 620 nm indicates the formation of new chromophoric species, which is also
confirmed by its peculiar resonance Raman spectrum at 632.8 nm wavelength. The in situ SAXS results
show that, during the anilinium polymerization in aqueous clay suspension, the interlayer spacing is ca.
19 Å. XRD diffraction pattern and SEM images of the powder PANI−MMT nanocomposites indicate that
the polymerization occurs mainly between the clay layers, and the basal spacing is ca. 13.2 Å. While the
IR spectra of nanocomposites show only bands due to PANI−ES-like segments, resonance Raman and
nitrogen XANES techniques lead to the presence of PANI−ES-like chains, benzidine segments, azo bonds,
and phenazine-like rings in the structure of the confined conducting polymers. The XPS technique detects
only PANI−ES segments of the polymeric structure, suggesting that on the external surface and/or on
the edge of clay crystal they are predominant in the chains.
One-dimensional diamondoid polyaniline-like nanothreads combine the outstanding mechanical properties of carbon nanotubes with the versatility of NH2 groups.
Microorganism pathogenicity strongly relies on the generation of multicellular assemblies, called biofilms. Understanding their organization can unveil vulnerabilities leading to potential treatments; spatially and temporally-resolved comprehensive experimental characterization can provide new details of biofilm formation, and possibly new targets for disease control. Here, biofilm formation of economically important phytopathogen Xylella fastidiosa was analyzed at single-cell resolution using nanometer-resolution spectro-microscopy techniques, addressing the role of different types of extracellular polymeric substances (EPS) at each stage of the entire bacterial life cycle. Single cell adhesion is caused by unspecific electrostatic interactions through proteins at the cell polar region, where EPS accumulation is required for more firmly-attached, irreversibly adhered cells. Subsequently, bacteria form clusters, which are embedded in secreted loosely-bound EPS, and bridged by up to ten-fold elongated cells that form the biofilm framework. During biofilm maturation, soluble EPS forms a filamentous matrix that facilitates cell adhesion and provides mechanical support, while the biofilm keeps anchored by few cells. This floating architecture maximizes nutrient distribution while allowing detachment upon larger shear stresses; it thus complies with biological requirements of the bacteria life cycle. Using new approaches, our findings provide insights regarding different aspects of the adhesion process of X. fastidiosa and biofilm formation.
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