POSS-Appended Diphenylalanine: Self-Cleaning, Pollution-Protective, and Fire-Retardant Hybrid Molecular Material.
ABSTRACT: Ordered self-assemblies of hybrid molecules have potential as protective umbrellas against environmental pollution and corrosion. This article describes the design and fabrication of a new self-cleaning hybrid molecular material containing polyhedral oligomeric silsesquioxane (POSS) and diphenylalanine as hydrophobic and pollution-protective coating. The colorless organic-inorganic hybrid materials, in which the diphenylalanine motif controls the self-assembly, exhibit unique water resistance property and enhance mechanical strength of paper 1.5-fold. The hybrid building blocks self-assemble in antiparallel sheet manner through noncovalent interactions to form a supramolecular layerlike surface with enhanced roughness. The hybrid material is soluble in organic solvents at room temperature that makes it easy to coat on paper, wood, or metal surfaces. The coating is effective against rusting, corrosion, environmental pollution, and bacterial attack. The coating has been used as fire retardant and enhances fire safety. The sustainable molecular material is promising for the packaging industry and metal industry and artifact preservation.
Project description:Controlling the self-assembly of diphenylalanine peptide (FF) into various nanoarchitectures has received great amounts of attention in recent years. Here, we report the temperature-induced reversible self-assembly of diphenylalanine peptide to microtubes, nanowires, or organogel in different solvents. We also find that the organogel in isopropanol transforms into crystalline flakes or nanowires when the temperature increases. The reversible self-assembly in polar solvents may be mainly controlled by electronic and aromatic interactions between the FF molecules themselves, which is associated with the dissociation equilibrium and significantly influenced by temperature. We found that the organogel in the isopropanol solvent made a unique transition to crystalline structures, a process that is driven by temperature and may be kinetically controlled. During the heating-cooling process, FF preferentially self-assembles to metastable nanofibers and organogel. They further transform to thermodynamically stable crystal structures via molecular rearrangement after introducing an external energy, such as the increasing temperature used in this study. The strategy demonstrated in this study provides an efficient way to controllably fabricate smart, temperature-responsive peptide nanomaterials and enriches the understanding of the growth mechanism of diphenylalanine peptide nanostructures.
Project description:Peptides have attracted considerable attention due to their biocompatibility, functional molecular recognition and unique biological and electronic properties. The strong piezoelectricity in diphenylalanine peptide expands its technological potential as a smart material. However, its random and unswitchable polarization has been the roadblock to fulfilling its potential and hence the demonstration of a piezoelectric device remains lacking. Here we show the control of polarization with an electric field applied during the peptide self-assembly process. Uniform polarization is obtained in two opposite directions with an effective piezoelectric constant d33 reaching 17.9?pm?V-1. We demonstrate the power generation with a peptide-based power generator that produces an open-circuit voltage of 1.4?V and a power density of 3.3?nW?cm-2. Devices enabled by peptides with controlled piezoelectricity provide a renewable and biocompatible energy source for biomedical applications and open up a portal to the next generation of multi-functional electronics compatible with human tissue.
Project description:Highly loaded polymer/clay nanocomposites with layered structures are emerging as robust fire retardant surface coatings. However, time-intensive sequential deposition processes, e.g. layer-by-layer strategies, hinders obtaining large coating thicknesses and complicates an implementation into existing technologies. Here, we demonstrate a single-step, water-borne approach to prepare thick, self-assembling, hybrid fire barrier coatings of sodium carboxymethyl cellulose (CMC)/montmorillonite (MTM) with well-defined, bioinspired brick-wall nanostructure, and showcase their application on textile. The coating thickness on the textile is tailored using different concentrations of CMC/MTM (1-5?wt%) in the coating bath. While lower concentrations impart conformal coatings of fibers, thicker continuous coatings are obtained on the textile surface from highest concentration. Comprehensive fire barrier and fire retardancy tests elucidate the increasing fire barrier and retardancy properties with increasing coating thickness. The materials are free of halogen and heavy metal atoms, and are sourced from sustainable and partly even renewable building blocks. We further introduce an amphiphobic surface modification on the coating to impart oil and water repellency, as well as self-cleaning features. Hence, our study presents a generic, environmentally friendly, scalable, and one-pot coating approach that can be introduced into existing technologies to prepare bioinspired, thick, fire barrier nanocomposite coatings on diverse surfaces.
Project description:Self-assembly of fluorenylmethoxycarbonyl-protected diphenylalanine (FmocFF) in water is widely known to produce hydrogels. Typically, confocal microscopy is used to visualize such hydrogels under wet conditions, that is, without freezing or drying. However, key aspects of hydrogels like fiber diameter, network morphology and mesh size are sub-diffraction limited features and cannot be visualized effectively using this approach. In this work, we show that it is possible to image FmocFF hydrogels by Points Accumulation for Imaging in Nanoscale Topography (PAINT) in native conditions and without direct gel labelling. We demonstrate that the fiber network can be visualized with improved resolution (?50?nm) both in 2D and 3D. Quantitative information is extracted such as mesh size and fiber diameter. This method can complement the existing characterization tools for hydrogels and provide useful information supporting the design of new materials.
Project description:The anti-corrosion performances of single(TEOS) and hybrid (APTES-TEOS) sol-gel coatings on Al alloy samples exposed to 3.5?wt% NaCl were evaluated employing electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The data acquired using the three corrosion analysis techniques were in accordance with each other where hybrid sol-gel coating offered the lowest corrosion rate and current density in comparison to the single precursor silanol coating. Tafel curves suggested that the hybrid silane coatings mitigate both the anodic and cathodic reactions simultaneously (mixed type inhibitor). These techniques justified that incorporation of hybrid sol-gel improved the Al corrosion protection performance considerably.
Project description:Using small angle neutron scattering (SANS), it is shown that the existence of pre-assembled structures at high pH for a capped diphenylalanine hydrogel is controlled by the selection of N-terminal heterocyclic capping group, namely indole or carbazole. At high pH, changing from a somewhat hydrophilic indole capping group to a more hydrophobic carbazole capping group results in a shift from a high proportion of monomers to self-assembled fibers or wormlike micelles. The presence of these different self-assembled structures at high pH is confirmed through NMR and circular dichroism spectroscopy, scanning probe microscopy and cryogenic transmission electron microscopy.
Project description:UV irradiation of aligned diphenylalanine peptide nanotubes (FF-PNTs) decorated with plasmonic silver nanoparticles (Ag NPs) enables photo-induced surface-enhanced Raman spectroscopy. UV-induced charge transfer facilitates a chemical enhancement that provides up to a 10-fold increase in surface-enhanced Raman intensity and allows the detection of a wide range of small molecules and low Raman cross-section molecules at concentrations as low as 10-13?M. The aligned FF-PNT/Ag NP template further prevents photodegradation of the molecules under investigation. Our results demonstrate that FF-PNTs can be used as an alternative material to semiconductors such as titanium dioxide for photo-induced surface-enhanced Raman spectroscopy applications.
Project description:Gold-based nanomaterials have attracted extensive interest for potential application in photothermal therapy (PTT) owing to their distinctive properties including high photothermal transduction, biocompatibility, and low cytotoxicity. Herein, assembled gold nanoparticle architecture-based photothermal conversion agents were synthesized by using polysaccharides (alginate dialdehyde, ADA) as both the cross-linker to induce self-assembly of diphenylalanine (FF) and the reducer for in situ reduction of Au3+ ions into Au nanoparticles (Au NPs). The extinction spectrum of the obtained self-assembled ADA-FF/Au nanospheres was finely modulated into a near-infrared region by controlling the growth of Au NPs inside the assemblies. The strong plasmonic coupling effect of the assembled Au NPs also leads to high photothermal conversion (? = 40%) of the ADA-FF/Au nanospheres, hence presenting good performance in PTT and photoacoustic imaging. This synthesis technique is promising to construct nanomaterials with desired functions for potential biomedical application by self-assembly of various nanocrystals in situ.
Project description:Due to their excellent biodegradability characteristics, Mg and Mg-based alloys have become an emerging material in biomedical implants, notably for repair of bone as well as coronary arterial stents. However, the main problem with Mg-based alloys is their rapid corrosion in aggressive environments such as human bodily fluids. Previously, many approaches such as control of alloying materials, composition and surface treatments, have been attempted to regulate the corrosion rate. This article presents a comprehensive review of recent research focusing on surface treatment techniques utilised to control the corrosion rate and surface integrity of Mg-based alloys in both in vitro and in vivo environments. Surface treatments generally involve the controlled deposition of thin film coatings using various coating processes, and mechanical surfacing such as machining, deep rolling or low plasticity burnishing. The aim is to either make a protective thin layer of a material or to change the micro-structure and mechanical properties at the surface and sub-surface levels, which will prevent rapid corrosion and thus delay the degradation of the alloys. We have organised the review of past works on coatings by categorising the coatings into two classes-conversion and deposition coatings-while works on mechanical treatments are reviewed based on the tool-based processes which affect the sub-surface microstructure and mechanical properties of the material. Various types of coatings and their processing techniques under two classes of coating and mechanical treatment approaches have been analysed and discussed to investigate their impact on the corrosion performance, biomechanical integrity, biocompatibility and cell viability. Potential challenges and future directions in designing and developing the improved biodegradable Mg/Mg-based alloy implants were addressed and discussed. The literature reveals that no solutions are yet complete and hence new and innovative approaches are required to leverage the benefit of Mg-based alloys. Hybrid treatments combining innovative biomimetic coating and mechanical processing would be regarded as a potentially promising way to tackle the corrosion problem. Synergetic cutting-burnishing integrated with cryogenic cooling may be another encouraging approach in this regard. More studies focusing on rigorous testing, evaluation and characterisation are needed to assess the efficacy of the methods.
Project description:Polyurea microcapsules with Ethylenediamine (EDA) as the core material were synthesized. A set of characterization methods, including optical and scanning electron microscopy (OM and SEM), the Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA) were used to confirm the microcapsule morphology and chemical structures. The influence of emulsifier content and stirring rate on size and morphology of the microcapsules was investigated, and the self-healing performance of EDA-Polyurea microcapsule/epoxy coatings was evaluated by electrochemical impedance spectroscopy (EIS) measurements. The results showed that the microcapsules obtained had good spherical shape with a mean diameter of 0.54-0.70 ?m. Compared with pure core material, the microcapsule showed excellent thermostability, and the content of core materials was up to 56.00 wt%. The epoxy coating with 5.0 wt% EDA-Polyurea microcapsules achieved average corrosion resistance efficiencies of 90.00%, significantly enhancing the capability of the scratched coating to resist external corrosion.