Thin films of 10,12-pentacosadiynoic acid were prepared using Langmuir and spin-coating techniques and polymerized using a controlled dosage of UV radiation. The radiation-induced phase transitions: from the colorless monomer, via the metastable blue phase, to the red polydiacetylene phase, and finally to degradation of the material, were monitored by optical absorbance spectroscopy. Deconvolution analysis of the absorbance curves allowed us to monitor quantitatively the dynamical changes in the chromatic properties of the films as a function of applied UV radiation dose. Several reaction kinetics models were applied in order to describe the phase transitions in the films. The results present the phase evolution in PDA and compare the kinetics for Langmuir films vs. spin-coated films. Polymerization directly at the air-water interface was found to be two-to-three orders of magnitude faster compared to solid-supported films of the same material. Moreover, we show that the data of the solid supported films is considerably better fitted when a reversible intermediate phase between the blue and the red phases is considered. Furthermore, a shift of the Raman active triple bond supports the presence of the intermediate phase.
Spectacular colors and visual phenomena in animals are produced by light interference from highly reflective guanine crystals. Little is known about how organisms regulate crystal morphology to tune the optics of these systems. By following guanine crystal formation in developing spiders, a crystallization mechanism is elucidated. Guanine crystallization is a “non‐classical,” multistep process involving a progressive ordering of states. Crystallization begins with nucleation of partially ordered nanogranules from a disordered precursor phase. Growth proceeds by orientated attachment of the nanogranules into platelets which coalesce into single crystals, via progressive relaxation of structural defects. Despite their prismatic morphology, the platelet texture is retained in the final crystals, which are composites of crystal lamellae and interlamellar sheets. Interactions between the macromolecular sheets and the planar face of guanine appear to direct nucleation, favoring platelet formation. These findings provide insights on how organisms control the morphology and optical properties of molecular crystals.
Amyloid protein fibrils and some antimicrobial peptides (AMPs) share biophysical and structural properties. This observation suggests that ordered self-assembly can act as an AMP-regulating mechanism, and, vice versa, that human amyloids play a role in host defense against pathogens, as opposed to their common association with neurodegenerative and systemic diseases. Based on previous structural information on toxic amyloid peptides, we developed a sequence-based bioinformatics platform and, led by its predictions, experimentally identified 14 fibril-forming AMPs (ffAMPs) from living organisms, which demonstrated cross-β and cross-α amyloid properties. The results support the amyloid–antimicrobial link. The high prevalence of ffAMPs produced by amphibians and marine creatures among other species suggests that they confer unique advantageous properties in distinctive environments, potentially providing stability and adherence properties. Most of the newly identified 14 ffAMPs showed lipid-induced and/or time-dependent secondary structure transitions in the fibril form, indicating structural and functional cross-α/β chameleons. Specifically, ffAMP cytotoxicity against human cells correlated with the inherent or lipid-induced α-helical fibril structure. The findings raise hypotheses about the role of fibril secondary structure switching in regulation of processes, such as the transition between a stable storage conformation and an active state with toxicity against specific cell types.
Polydiacetylene (PDA) Langmuir films (LF) containing Zn 2+ cations were prepared in different experimental procedures. The incorporation of zinc cations resulted in new morphological and spectral properties. We found that zinc cations stabilize the blue phase of PDA, and inhibit its transformation into the red phase, withstanding prolonged exposure to UV irradiation. The increased stability was accompanied with the loss of the linear strand morphology and appearance of a new, transient purple phase before the final red phase stage. It was found that the most significant differences in film properties occur when the zinc cations are already present in solution during the polymerization stage at sufficient concentration. In such case zinc ions penetrate into the headgroup interlayer in the trilayer organization, and are implicated in the film's chromatic properties. In cases where polymerization was carried out prior to introduction of the cations, the properties of PDA/Zn 2+ films are similar to films produced on a pure water subphase.
Biomineralization is a process that takes place in all domains of life and which usually helps organisms to harden soft tissues by creating inorganic structures that facilitate their biological functions. It was shown that biominerals are under tight biological control via proteins that are involved in nucleation initiation and/or which act as structural skeletons. Magnetotactic bacteria (MTB) use iron biomineralization to create nano-magnetic particles in a specialized organelle, the magnetosome, to align to the geomagnetic field. A specific set of magnetite-associated proteins (MAPs) is involved in regulating magnetite nucleation, size, and shape. These MAPs are all predicted to contain specific 17–22 residue-long sequences involved in magnetite formation. To understand the mechanism of magnetite formation, we focused on three different MAPs, MamC, Mms6 and Mms7, and studied the predicted iron-binding sequences. Using nuclear magnetic resonance (NMR), we differentiated the recognition mode of each MAP based on ion specificity, affinity, and binding residues. The significance of critical residues in each peptide was evaluated by mutation followed by an iron co-precipitation assay. Among the peptides, MamC showed weak ion binding but created the most significant effect in enhancing magnetite particle size, indicating the potency in controlling magnetite particle shape and size. Alternatively, Mms6 and Mms7 had strong binding affinities but less effect in modulating magnetite particle size, representing their major role potentially in initiating nucleation by increasing local metal concentration. Overall, our results explain how different MAPs affect magnetite synthesis, interact with Fe2+ ions and which residues are important for the MAPs functions.
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