Piezoelectric Peptide Nanotube Substrate Sensors Activated through Sound Wave Energy.

The use of sustainable and safe materials is increasingly in demand for the creation of photonic-based technology. Piezoelectric peptide nanotubes make up a class of safe and sustainable materials. We show that these materials can generate piezoelectric charge through the deformation of oriented molecular dipoles when the tube length is flexed through the application of sound energy. Through the combination of peptide nanotubes with plasmon active nanomaterials, harvesting of low-frequency acoustic sound waves was achieved. This effect was applied to boost surface-enhanced Raman scattering signal detection of analytes, including glucose. This work demonstrates the potential of utilizing sound to boost sensing by using piezoelectric materials.

Structural Transition-Induced Raman Enhancement in Bioinspired Diphenylalanine Peptide Nanotubes.

Semiconducting materials are increasingly proposed as alternatives to noble metal nanomaterials to enhance Raman scattering. We demonstrate that bioinspired semiconducting diphenylalanine peptide nanotubes annealed through a reported structural transition can support Raman detection of 10-7 M concentrations for a range of molecules including mononucleotides. The enhancement is attributed to the introduction of electronic states below the conduction band that facilitate charge transfer to the analyte molecule. These results show that organic semiconductor-based materials can serve as platforms for enhanced Raman scattering for chemical sensing. As the sensor is metal-free, the enhancement is achieved without the introduction of electromagnetic surface-enhanced Raman spectroscopy.

Electric Field Tunability of Photoluminescence from a Hybrid Peptide-Plasmonic Metal Microfabricated Chip.

Enhancement of fluorescence through the application of plasmonic metal nanostructures has gained substantial research attention due to the widespread use of fluorescence-based measurements and devices. Using a microfabricated plasmonic silver nanoparticle-organic semiconductor platform, we show experimentally the enhancement of fluorescence intensity achieved through electro-optical synergy. Fluorophores located sufficiently near silver nanoparticles are combined with diphenylalanine nanotubes (FFNTs) and subjected to a DC electric field. It is proposed that the enhancement of the fluorescence signal arises from the application of the electric field along the length of the FFNTs, which stimulates the pairing of low-energy electrons in the FFNTs with the silver nanoparticles, enabling charge transport across the metal-semiconductor template that enhances the electromagnetic field of the plasmonic nanoparticles. Many-body perturbation theory calculations indicate that, furthermore, the charging of silver may enhance its plasmonic performance intrinsically at particular wavelengths, through band-structure effects. These studies demonstrate for the first time that field-activated plasmonic hybrid platforms can improve fluorescence-based detection beyond using plasmonic nanoparticles alone. In order to widen the use of this hybrid platform, we have applied it to enhance fluorescence from bovine serum albumin and Pseudomonas fluorescens. Significant enhancement in fluorescence intensity was observed from both. The results obtained can provide a reference to be used in the development of biochemical sensors based on surface-enhanced fluorescence.

Flexing Piezoelectric Diphenylalanine-Plasmonic Metal Nanocomposites to Increase SERS Signal Strength.

Piezoelectric quasi-1D peptide nanotubes and plasmonic metal nanoparticles are combined to create a flexible and self-energized surface-enhanced Raman spectroscopy (SERS) substrate that strengthens SERS signal intensities by over an order of magnitude compared to an unflexed substrate. The platform is used to sense bovine serum albumin, lysozyme, glucose, and adenine. Finite-element electromagnetic modeling indicates that the signal enhancement results from piezoelectric-induced charge, which is mechanically activated via substrate bending. The results presented here open the possibility of using peptide nanotubes on conformal substrates for in situ SERS detection.

Enhanced photocatalysis and biomolecular sensing with field-activated nanotube-nanoparticle templates.

The development of new catalysts for oxidation reactions is of central importance for many industrial processes. Plasmonic catalysis involves photoexcitation of templates/chips to drive and enhance oxidation of target molecules. Raman-based sensing of target molecules can also be enhanced by these templates. This provides motivation for the rational design, characterization, and experimental demonstration of effective template nanostructures. In this paper, we report on a template comprising silver nanoparticles on aligned peptide nanotubes, contacted with a microfabricated chip in a dry environment. Efficient plasmonic catalysis for oxidation of molecules such as p-aminothiophenol results from facile trans-template charge transfer, activated and controlled by application of an electric field. Raman detection of biomolecules such as glucose and nucleobases are also dramatically enhanced by the template. A reduced quantum mechanical model is formulated, comprising a minimum description of key components. Calculated nanotube-metal-molecule charge transfer is used to understand the catalytic mechanism and shows this system is well-optimized.

Electric Field-Induced Chemical Surface-Enhanced Raman Spectroscopy Enhancement from Aligned Peptide Nanotube-Graphene Oxide Templates for Universal Trace Detection of Biomolecules.

Semiconductor-graphene oxide-based surface-enhanced Raman spectroscopy substrates represent a new frontier in the field of surface-enhanced Raman spectroscopy (SERS). However, the application of graphene oxide has had limited success because of the poor Raman enhancement factors that are achievable in comparison to noble metals. In this work, we report chemical SERS enhancement enabled by the application of an electric field (10-25 V/mm) to aligned semiconducting peptide nanotube-graphene oxide composite structures during Raman measurements. The technique enables nanomolar detection sensitivity of glucose and nucleobases with up to 10-fold signal enhancement compared to metal-based substrates, which, to our knowledge, is higher than that previously reported for semiconductor-based SERS substrates. The increased Raman scattering is assigned to enhanced charge-transfer resonance enabled by work function lowering of the peptide nanotubes. These results provide insight into how semiconductor organic peptide nanotubes interact with graphene oxide, which may facilitate chemical biosensing, electronic devices, and energy-harvesting applications.

Photo-induced surface-enhanced Raman spectroscopy from a diphenylalanine peptide nanotube-metal nanoparticle template.

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.