Thermally Tunable Ultrasensitive Infrared Absorption Spectroscopy Platforms Based on Thin Phase-Change Films

The thermal tunability of the optical and electrical properties of phase-change materials has enabled the decades-old rewritable optical data storage and the recently commercialized phase-change memory devices. Recently, phase-change materials, in particular, Ge₂Sb₂Te₅ (GST), have been considered for other thermally configurable photonics applications, such as active plasmonic surfaces. Here, we focus on nonplasmonic field enhancement and demonstrate the use of the phase-change materials in ultrasensitive infrared absorption spectroscopy platforms employing interference-based uniform field enhancement. The studied structures consist of patternless thin GST and metal films, enabling simple and large-area fabrication on rigid and flexible substrates. Crystallization of the as-fabricated amorphous GST layer by annealing tunes (redshifts) the field-enhancement wavelength range. The surfaces are tested with ultrathin chemical and biological probe materials. The measured absorption signals are found to be comparable or superior to the values reported for the ultrasensitive infrared absorption spectroscopy platforms based on plasmonic field-enhancement

Universal Infrared Absorption Spectroscopy Using Uniform Electromagnetic Enhancement

Infrared absorption spectroscopy has greatly benefited from the electromagnetic field enhancement offered by plasmonic surfaces. However, because of the localized nature of plasmonic fields, such field enhancements are limited to nanometer-scale volumes. Here, we demonstrate that a relatively small, but spatially uniform field enhancement can yield a superior infrared detection performance compared to the plasmonic field enhancement exhibited by optimized infrared nanoantennas. A specifically designed CaF₂/Al thin film surface is shown to enable observation of stronger vibrational signals from the probe material, with wider bandwidth and a deeper spatial extent of the field enhancement as compared to such plasmonic surfaces. It is demonstrated that the surface structure presented here can enable chemically specific and label-free detection of organic monolayers using surface-enhanced infrared spectroscopy, indicating a great potential in highly sensitive yet cost-effective biomolecular sensing applications

Counting Molecules with a Mobile Phone Camera Using Plasmonic Enhancement

Plasmonic field enhancement enables the acquisition of Raman spectra at a single molecule level. Here we investigate the detection of surface enhanced Raman signal using the unmodified image sensor of a smart phone, integrated onto a confocal Raman system. The sensitivity of a contemporary smart phone camera is compared to a photomultiplier and a cooled charge-coupled device. The camera displays a remarkably high sensitivity, enabling the observation of the weak unenhanced Raman scattering signal from a silicon surface, as well as from liquids, such as ethanol. Using high performance wide area plasmonic substrates that enhance the Raman signal 10⁶ to 10⁷ times, blink events typically associated with single molecule motion, are observed on the smart phone camera. Raman spectra can also be collected on the smart phone by converting the camera into a low resolution spectrometer with the inclusion of a collimator and a dispersive optical element in front of the camera. In this way, spectral content of the blink events can be observed on the plasmonic substrate, in real time, at 30 frames per second

Counting Molecules with a Mobile Phone Camera Using Plasmonic Enhancement

Plasmonic field enhancement enables the acquisition of Raman spectra at a single molecule level. Here we investigate the detection of surface enhanced Raman signal using the unmodified image sensor of a smart phone, integrated onto a confocal Raman system. The sensitivity of a contemporary smart phone camera is compared to a photomultiplier and a cooled charge-coupled device. The camera displays a remarkably high sensitivity, enabling the observation of the weak unenhanced Raman scattering signal from a silicon surface, as well as from liquids, such as ethanol. Using high performance wide area plasmonic substrates that enhance the Raman signal 10⁶ to 10⁷ times, blink events typically associated with single molecule motion, are observed on the smart phone camera. Raman spectra can also be collected on the smart phone by converting the camera into a low resolution spectrometer with the inclusion of a collimator and a dispersive optical element in front of the camera. In this way, spectral content of the blink events can be observed on the plasmonic substrate, in real time, at 30 frames per second

Counting Molecules with a Mobile Phone Camera Using Plasmonic Enhancement

Plasmonic field enhancement enables the acquisition of Raman spectra at a single molecule level. Here we investigate the detection of surface enhanced Raman signal using the unmodified image sensor of a smart phone, integrated onto a confocal Raman system. The sensitivity of a contemporary smart phone camera is compared to a photomultiplier and a cooled charge-coupled device. The camera displays a remarkably high sensitivity, enabling the observation of the weak unenhanced Raman scattering signal from a silicon surface, as well as from liquids, such as ethanol. Using high performance wide area plasmonic substrates that enhance the Raman signal 10⁶ to 10⁷ times, blink events typically associated with single molecule motion, are observed on the smart phone camera. Raman spectra can also be collected on the smart phone by converting the camera into a low resolution spectrometer with the inclusion of a collimator and a dispersive optical element in front of the camera. In this way, spectral content of the blink events can be observed on the plasmonic substrate, in real time, at 30 frames per second

Counting Molecules with a Mobile Phone Camera Using Plasmonic Enhancement

Plasmonic field enhancement enables the acquisition of Raman spectra at a single molecule level. Here we investigate the detection of surface enhanced Raman signal using the unmodified image sensor of a smart phone, integrated onto a confocal Raman system. The sensitivity of a contemporary smart phone camera is compared to a photomultiplier and a cooled charge-coupled device. The camera displays a remarkably high sensitivity, enabling the observation of the weak unenhanced Raman scattering signal from a silicon surface, as well as from liquids, such as ethanol. Using high performance wide area plasmonic substrates that enhance the Raman signal 10⁶ to 10⁷ times, blink events typically associated with single molecule motion, are observed on the smart phone camera. Raman spectra can also be collected on the smart phone by converting the camera into a low resolution spectrometer with the inclusion of a collimator and a dispersive optical element in front of the camera. In this way, spectral content of the blink events can be observed on the plasmonic substrate, in real time, at 30 frames per second

Exploiting Native Al₂O₃ for Multispectral Aluminum Plasmonics

Aluminum, despite its abundance and low cost, is usually avoided for plasmonic applications due to losses in visible/infrared regimes and its interband absorption at 800 nm. Yet, it is compatible with silicon CMOS processes, making it a promising alternative for integrated plasmonic applications. It is also well known that a thin layer of native Al₂O₃ is formed on aluminum when exposed to air, which must be taken into account properly while designing plasmonic structures. Here, for the first time we report exploitation of the native Al₂O₃ layer for fabrication of periodic metal–insulator–metal (MIM) plasmonic structures that exhibit resonances spanning a wide spectral range, from the near-ultraviolet to mid-infrared region of the spectrum. Through fabrication of silver nanoislands on aluminum surfaces and MIM plasmonic surfaces with a thin native Al₂O₃ layer, hierarchical plasmonic structures are formed and used in surface-enhanced infrared spectroscopy (SEIRA) and surface-enhanced Raman spectrocopy (SERS) for detection of self-assembled monolayers of dodecanethiol

Multivalent Presentation of Cationic Peptides on Supramolecular Nanofibers for Antimicrobial Activity

Noncovalent and electrostatic interactions facilitate the formation of complex networks through molecular self-assembly in biomolecules such as proteins and glycosaminoglycans. Self-assembling peptide amphiphiles (PA) are a group of molecules that can form nanofibrous structures and may contain bioactive epitopes to interact specifically with target molecules. Here, we report the presentation of cationic peptide sequences on supramolecular nanofibers formed by self-assembling peptide amphiphiles for cooperative enhanced antibacterial activity. Antibacterial properties of self-assembled peptide nanofibers were significantly higher than soluble peptide molecules with identical amino acid sequences, suggesting that the tandem presentation of bioactive epitopes is important for designing new materials for bactericidal activity. In addition, bacteria were observed to accumulate more rapidly on peptide nanofibers compared to soluble peptides, which may further enhance antibacterial activity by increasing the number of peptide molecules interacting with the bacterial membrane. The cationic peptide amphiphile nanofibers were observed to attach to bacterial membranes and disrupt their integrity. These results demonstrate that short cationic peptides show a significant improvement in antibacterial activity when presented in the nanofiber form

Fabrication of Supramolecular n/p-Nanowires <i>via</i> Coassembly of Oppositely Charged Peptide-Chromophore Systems in Aqueous Media

Fabrication of supramolecular electroactive materials at the nanoscale with well-defined size, shape, composition, and organization in aqueous medium is a current challenge. Herein we report construction of supramolecular charge-transfer complex one-dimensional (1D) nanowires consisting of highly ordered mixed-stack π-electron donor–acceptor (D–A) domains. We synthesized n-type and p-type β-sheet forming short peptide-chromophore conjugates, which assemble separately into well-ordered nanofibers in aqueous media. These complementary p-type and n-type nanofibers coassemble <i>via</i> hydrogen bonding, charge-transfer complex, and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This molecular design ensures highly ordered arrangement of D–A stacks within n/p-coassembled supramolecular nanowires. The supramolecular n/p-coassembled nanowires were found to be formed by A–D–A unit cells having an association constant (<i>K</i>_A) of 5.18 × 10⁵ M^–1. In addition, electrical measurements revealed that supramolecular n/p-coassembled nanowires are approximately 2400 and 10 times more conductive than individual n-type and p-type nanofibers, respectively. This facile strategy allows fabrication of well-defined supramolecular electroactive nanomaterials in aqueous media, which can find a variety of applications in optoelectronics, photovoltaics, organic chromophore arrays, and bioelectronics

Biocompatible Electroactive Tetra(aniline)-Conjugated Peptide Nanofibers for Neural Differentiation

Peripheral nerve injuries cause devastating problems for the quality of patients’ lives, and regeneration following damage to the peripheral nervous system is limited depending on the degree of the damage. Use of nanobiomaterials can provide therapeutic approaches for the treatment of peripheral nerve injuries. Electroactive biomaterials, in particular, can provide a promising cure for the regeneration of nerve defects. Here, a supramolecular electroactive nanosystem with tetra­(aniline) (TA)-containing peptide nanofibers was developed and utilized for nerve regeneration. Self-assembled TA-conjugated peptide nanofibers demonstrated electroactive behavior. The electroactive self-assembled peptide nanofibers formed a well-defined three-dimensional nanofiber network mimicking the extracellular matrix of the neuronal cells. Neurite outgrowth was improved on the electroactive TA nanofiber gels. The neural differentiation of PC-12 cells was more advanced on electroactive peptide nanofiber gels, and these biomaterials are promising for further use in therapeutic neural regeneration applications