Development of High Surface Area Organosilicate Nanoparticulate Thin Films for Use in Sensing Hydrophobic Compounds in Sediment and Water.

The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m2/g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (Kow) greater than four; however, surface modification of these particles would be required for application to other chemicals.

Spallation of Isolated Aluminum Nanoparticles by Rapid Photothermal Heating.

The spallation of isolated aluminum (Al) nanoparticles (NPs) is initiated using rapid photothermal heating. The Al NPs exhibited a nominal diameter of 120 nm, with an average oxide shell thickness of 3.8 nm. Photothermal heating was achieved by coupling a focused laser (446 nm wavelength) to an optical grating substrate and to the plasmonic resonance of the Al NPs themselves. These factors enhanced the absorption cross section by a factor of 8-18 compared to no substrate and generated an Al NP heating rate on the order of 107-108 K/s. Observations indicate that molten Al is ejected from the heated NP, indicating that melting of the Al core is required for spallation. A graphene layer atop the grating substrate encouraged the formation of discrete particles of ejected Al, while irregular elongated filament products were observed without the graphene layer. Numerical simulations indicate that laser-heated Al NPs reach temperatures between approximately 1000 and 1500 K. These observations and experimental conditions are consistent with those anticipated for the melt dispersion mechanism, a thermomechanical reaction mechanism that has not previously been clearly demonstrated. Activating and controlling this mechanism is anticipated to enhance applications ranging from biological phototherapy to energetic materials.

Applications of machine learning tools for ultra-sensitive detection of lipoarabinomannan with plasmonic grating biosensors in clinical samples of tuberculosis.

BACKGROUND: Tuberculosis is one of the top ten causes of death globally and the leading cause of death from a single infectious agent. Eradicating the Tuberculosis epidemic by 2030 is one of the top United Nations Sustainable Development Goals. Early diagnosis is essential to achieving this goal because it improves individual prognosis and reduces transmission rates of asymptomatic infected. We aim to support this goal by developing rapid and sensitive diagnostics using machine learning algorithms to minimize the need for expert intervention. METHODS AND FINDINGS: A single molecule fluorescence immunosorbent assay was used to detect Tuberculosis biomarker lipoarabinomannan from a set of twenty clinical patient samples and a control set of spiked human urine. Tuberculosis status was separately confirmed by GeneXpert MTB/RIF and cell culture. Two machine learning algorithms, an automatic and a semiautomatic model, were developed and trained by the calibrated lipoarabinomannan titration assay data and then tested against the ground truth patient data. The semiautomatic model differed from the automatic model by an expert review step in the former, which calibrated the lower threshold to determine single molecules from background noise. The semiautomatic model was found to provide 88.89% clinical sensitivity, while the automatic model resulted in 77.78% clinical sensitivity. CONCLUSIONS: The semiautomatic model outperformed the automatic model in clinical sensitivity as a result of the expert intervention applied during calibration and both models vastly outperformed manual expert counting in terms of time-to-detection and completion of analysis. Meanwhile, the clinical sensitivity of the automatic model could be improved significantly with a larger training dataset. In short, semiautomatic, and automatic Gaussian Mixture Models have a place in supporting rapid detection of Tuberculosis in resource-limited settings without sacrificing clinical sensitivity.

Laser-scribed conductive, photoactive transition metal oxide on soft elastomers for Janus on-skin electronics and soft actuators.

Laser-assisted fabrication of conductive materials on flexible substrates has attracted intense interests because of its simplicity, easy customization, and broad applications. However, it remains challenging to achieve laser scribing of conductive materials on tissue-like soft elastomers, which can serve as the basis to construct bioelectronics and soft actuators. Here, we report laser scribing of metallic conductive, photoactive transition metal oxide (molybdenum dioxide) on soft elastomers, coated with molybdenum chloride precursors, under ambient conditions. Laser-scribed molybdenum dioxide (LSM) exhibits high electrical conductivity, biocompatibility, chemical stability, and compatibility with magnetic resonance imaging. In addition, LSM can be made on various substrates (polyimide, glass, and hair), showing high generality. Furthermore, LSM-based Janus on-skin electronics are developed to record information from human skin, human breath, and environments. Taking advantage of its outstanding photothermal effect, LSM-based soft actuators are developed to build light-driven reconfigurable three-dimensional architectures, reshapable airflow sensors, and smart robotic worms with bioelectronic sensors.

Surface Plasmon Enhanced Fluorescence Temperature Mapping of Aluminum Nanoparticle Heated by Laser.

Partially aggregated Rhodamine 6G (R6G) dye is used as a lights-on temperature sensor to analyze the spatiotemporal heating of aluminum nanoparticles (Al NPs) embedded within a tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride (THV) fluoropolymer matrix. The embedded Al NPs were photothermally heated using an IR laser, and the fluorescent intensity of the embedded dye was monitored in real time using an optical microscope. A plasmonic grating substrate enhanced the florescence intensity of the dye while increasing the optical resolution and heating rate of Al NPs. The fluorescence intensity was converted to temperature maps via controlled calibration. The experimental temperature profiles were used to determine the Al NP heat generation rate. Partially aggregated R6G dyes, combined with the optical benefits of a plasmonic grating, offered robust temperature sensing with sub-micron spatial resolution and temperature resolution on the order of 0.2 °C.

Synchronized Electromechanical Shock Wave-Induced Bacterial Transformation.

We report a simple device that generates synchronized mechanical and electrical pressure waves for carrying out bacterial transformation. The mechanical pressure waves are produced by igniting a confined nanoenergetic composite material that provides ultrahigh pressure. Further, this device has an arrangement through which a synchronized electric field (of a time-varying nature) is initiated at a delay of ≈85 µs at the full width half-maxima point of the pressure pulse. The pressure waves so generated are incident to a thin aluminum-polydimethylsiloxane membrane that partitions the ignition chamber from the column of the mixture containing bacterial cells (Escherichia coli BL21) and 4 kb transforming DNA. A combination of mechanical and electrical pressure pulse created through the above arrangement ensures that the transforming DNA transports across the cell membrane into the cell, leading to a transformation event. This unique device has been successfully operated for efficient gene (∼4 kb) transfer into cells. The transformation efficacy of this device is found comparable to the other standard methods and protocols for carrying out the transformation.

Spontaneous emission rate enhancement with aperiodic Thue-Morse multilayer.

The emergence of multilayer metamaterials in the research field of enhancing spontaneous emission rates has recently received extensive attention. Previous research efforts mostly focus on periodic metal-dielectric multilayers in hyperbolic dispersion region; however, the influence of lattice order in subwavelength multilayers on spontaneous emission is rarely studied. Here, we observe the stronger Purcell enhancement of quantum dots coupled to the aperiodic metal-dielectric multilayer with Thue-Morse lattice order from elliptical to hyperbolic dispersion regions, compared to the periodic multilayer with the same metal filling ratio. This work demonstrates the potential of utilizing quasiperiodic metamaterial nanostructures to engineer the local density of states for various nanophotonic applications.

Ultrasensitive detection of lipoarabinomannan with plasmonic grating biosensors in clinical samples of HIV negative patients with tuberculosis.

BACKGROUND: Timely diagnosis of tuberculosis disease is critical for positive patient outcomes, yet potentially millions go undiagnosed or unreported each year. Sputum is widely used as the testing input, but limited by its complexity, heterogeneity, and sourcing problems. Finding methods to interrogate noninvasive, non-sputum clinical specimens is indispensable to improving access to tuberculosis diagnosis and care. In this work, economical plasmonic gratings were used to analyze tuberculosis biomarker lipoarabinomannan (LAM) from clinical urine samples by single molecule fluorescence assay (FLISA) and compared with gold standard sputum GeneXpert MTB/ RIF, culture, and reference ELISA testing results. METHODS AND FINDINGS: In this study, twenty sputum and urine sample sets were selected retrospectively from a repository of HIV-negative patient samples collected before initiation of anti-tuberculosis therapy. GeneXpert MTB/RIF and culture testing of patient sputum confirmed the presence or absence of pulmonary tuberculosis while all patient urines were reference ELISA LAM-negative. Plasmonic gratings produced by low-cost soft lithography were bound with anti-LAM capture antibody, incubated with patient urine samples, and biotinylated detection antibody. Fluorescently labeled streptavidin revealed single molecule emission by epifluorescence microscope. Using a 1 fg/mL baseline for limit of detection, single molecule FLISA demonstrated good qualitative agreement with gold standard tests on 19 of 20 patients, including accurately predicting the gold-standard-negative patients, while one gold-standard-positive patient produced no observable LAM in urine. CONCLUSIONS: Single molecule FLISA by plasmonic grating demonstrated the ability to quantify tuberculosis LAM from complex urine samples of patients from a high endemic setting with negligible interference from the complex media itself. Moreover, agreement with patient diagnoses by gold standard testing suggests that single molecule FLISA could be used as a highly sensitive test to diagnose tuberculosis noninvasively.

Linear Polyethylenimine-DNA Nanoconstruct for Corneal Gene Delivery.

PURPOSE: This study investigated the efficiency and potential toxicity of a linear 22-kDa polyethylenimine (PEI)-DNA nanoconstruct for delivering genes to corneal cells and the effects of PEI nitrogen-to-DNA phosphate (N:P) ratio on gene transfer efficiency in vitro and in vivo. METHODS: A gel retardation assay, zeta potential measurement, bright-field microscopy, transfection with green fluorescent protein (GFP), immunofluorescence, and enzyme-linked immunosorbent assay (ELISA) were used to characterize the physicochemical and biological properties and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), lactate dehydrogenase (LDH), and reactive oxygen species (ROS) assay for cytotoxicity of the linear PEI-DNA nanoconstruct using in vitro cultured primary human corneal fibroblast and in vivo mouse models. RESULTS: Of the several evaluated N:P ratios, the highest gene transfection efficiency achieved without any notable cytotoxicity was observed at an N:P ratio of 30:1 (N:P 30). In vivo gene transfer studies revealed substantial GFP gene delivery into the corneas of mice 3 days after a single 5-min topical application without any significant adverse ocular effects. Slit-lamp biomicroscope ophthalmic examination of the mouse exposed to the linear PEI-DNA nanoconstruct showed no evidence of hyperemia (redness), corneal edema, ocular inflammation, or epiphora (excessive tearing). CONCLUSIONS: The 22-kDa linear PEI-DNA nanoconstruct is an efficient and well-tolerated vector for corneal gene therapy in vitro and in vivo and could be used as a platform for developing novel gene-based nanomedicine approaches for corneal diseases.

Nanoscale surface reactions by laser irradiation of Al nanoparticles on MoO3 flakes.

Surface reactions between heated aluminum nanoparticles (Al NPs) and thin α-MoO3 sheets are investigated. Localized photothermal heating on Al NP clusters is provided by a Raman spectrometer laser, while enhanced heating rates and imaging resolution are enabled by the use of a plasmonic grating substrate. Prominent linear reaction zones extending from Al NPs in the 〈001〉 crystal direction are observed on the surface of the host MoO3 sheets after heating. Raman spectroscopy and x-ray diffraction indicate that α-Al2O3 is generated within these extended reacted regions, while AFM and SEM indicate that the topology of the reaction regions are indistinguishable from the MoO3 host. We hypothesize that these Al2O3 zones are formed by surface diffusion and subsequent sub-surface adsorption of heated Al adatoms along the low-energy 〈001〉 MoO3 direction. Understanding and controlling these reaction mechanisms could lead to enhanced combustion of Al/MoO3 nanothermite systems.

Enhanced fluorescence for in situ temperature mapping of photothermally heated aluminum nanoparticles enabled by a plasmonic grating substrate.

In situ dynamic temperature mapping of photothermally heated aluminum nanoparticles (Al NPs) embedded in a fluoropolymer (THV) is achieved using fluorescent dye (rhodamine 6G). A plasmonic grating substrate enhances the dye fluorescence intensity by a factor of seven over a glass substrate, to enable image capture rates of 500 frames per second. Further, the fluorescence intensity is linearly related to temperature and reversible. Photothermal heating of embedded Al NPs using a 2380 W cm-2 incident flux produced an Al NP heating rate of 1.2 × 104 °C s-1. Localized Al NP motion was also observed and attributed to thermal expansion and melting of the polymer. Multiphysics simulation provided agreement with experimental observations, bolstering confidence in the technique. The plasmonic grating platforms were shown to significantly improve both fluorescence intensity and the photothermal heating of Al compared to glass substrates, opening a new path for fast and high-resolution in situ temperature mapping.

Ultra-broadband infrared absorption by tapered hyperbolic multilayer waveguides.

Ultra-broadband strong absorption over 92% covering the infrared wavelength range of 1~6µm is demonstrated by using the tapered hyperbolic Au-SiO2 multilayer waveguides on glass substrates. Such broadband absorption is formed by the stop-light modes at various wavelengths located at different waveguide widths. A planar hyperbolic waveguide model is built to determine the stop-light modes by considering both forward and backward guided modes. The stop-light modes located inside the Au-SiO2 multilayer waveguide are simulated at the absorption peaks by reducing the Au loss. Tapered multilayer waveguides with varying top widths are further simulated, fabricated and measured, indicating the almost linear relation between the waveguide width and the stop-light wavelength. Moreover, the broadband absorption of tapered waveguide is proved to be angle-insensitive and polarization-independent, and the heat generation and temperature increase are also discussed.

In Situ Characterization of Photothermal Nanoenergetic Combustion on a Plasmonic Microchip.

Plasmonic gratings facilitate a robust in situ diagnostic platform for photothermal combustion of nanoenergetic composite thin films using an optical microscope and a high-speed camera. Aluminum nanoparticles (Al NPs) embedded in a fluoropolymer oxidizer are cast onto a plasmonic grating microchip and ignited using a low-power laser. The plasmonic grating enhances both spatial resolution and sufficient photothermal coupling to combust small Al NP clusters, initiating localized flames as small as 600 nm in size. Two-color pyrometry obtained from a high-speed color camera indicates an average flame temperature of 3900 K. Scattering measurements using polarized light microscopy enabled precise identification of individual Al NPs over a large field of view, leading to 3D reconstruction of combustion events.

Single-Molecule Surface Plasmon-Coupled Emission with Plasmonic Gratings.

The ability to image single molecules (SM) has been the dream of scientists for centuries, and because of the substantial recent advances in microscopy, individual fluorescent molecules can now be observed on a regular basis. However, the development of such imaging systems was not without dilemmas, such as the detection and separation of individual fluorescence emissions. One method to solve this problem utilized surface plasmon resonance (SPR) to enhance the emission intensity of SMs. Although enhancing the SM emission intensity has yielded promising results, this method does not fully utilize the unique plasmonic properties that could vastly improve the SM imaging capabilities. Here, we use SPR excitation as well as surface plasmon-coupled emission from a high-definition digital versatile disc grating structure to image and identify different fluorophores using the angular emission of individual molecules. Our results have important implications for research in multiplexed SM spectroscopy and SM fluorescence imaging.

Plasmonic nano-protrusions: hierarchical nanostructures for single-molecule Raman spectroscopy.

Classical methods for enhancing the electromagnetic field from substrates for spectroscopic applications, such as surface-enhanced Raman spectroscopy (SERS), have involved the generation of hotspots through directed self-assembly of nanoparticles or by patterning nanoscale features using expensive nanolithography techniques. A novel large-area, cost-effective soft lithographic technique involving glancing angle deposition (GLAD) of silver on polymer gratings is reported here. This method produces hierarchical nanostructures with high enhancement factors capable of analyzing single-molecule SERS. The uniform ordered and patterned nanostructures provide extraordinary field enhancements that serve as excitatory hotspots and are herein interrogated by SERS. The high spatial homogeneity of the Raman signal and signal enhancement over a large area from a self-assembled monolayer (SAM) of 2-naphthalenethiol demonstrated the uniformity of the hotspots. The enhancement was shown to have a critical dependence on the underlying nanostructure via the surface energy landscape and GLAD angles for a fixed deposition thickness, as evidenced by atomic force microscopy and scanning electron microscopy surface analysis of the substrate. The nanostructured surface leads to an extremely concentrated electromagnetic field at sharp nanoscale peaks, here referred to as 'nano-protrusions', due to the coupling of surface plasmon resonance (SPR) with localized SPR. These nano-protrusions act as hotspots which provide Raman enhancement factors as high as 108 over a comparable SAM on silver. Comparison of our substrate with the commercial substrate Klarite™ shows higher signal enhancement and minimal signal variation with hotspot spatial distribution. By using the proper plasmon resonance angle corresponding to the laser source wavelength, further enhancement in signal intensity can be achieved. Single-molecule Raman spectra for rhodamine 6G are obtained from the best SERS substrate (a GLAD angle of 60°). The single-molecule spectrum is invariant over the substrate, due to the patterned ordered nanostructures (nano-protrusions).

Barrier Modification of Metal-contact on Silicon by Sub-2 nm Platinum Nanoparticles and Thin Dielectrics.

We report metal/p-Si contact barrier modification through the introduction of either "isolated" or "nonisolated" tilted-target-sputtered sub-2 nm platinum nanoparticles (Pt NPs) in combination with either a 0.98 nm Atomic Layer Deposited Al2O3 or a 1.6 nm chemically grown SiO2 dielectric layer, or both. Here, we study the role of these Pt NP's size dependent properties, i.e., the Pt NP-metal surface dipole, the Coulomb blockade and quantum confinement effect in determining the degree of Fermi level depinning observed at the studied metal/p-Si interfaces. By varying only the embedded Pt NP size and its areal density, the nature of the contact can also be modulated to be either Schottky or Ohmic upon utilizing the same gate metal. 0.74 nm Pt NPs with an areal density of 1.1 × 10(13) cm(-2) show ~382 times higher current densities compared to the control sample embedded with similarly sized Pt NPs with ~1.6 times lower areal densities. We further demonstrate that both Schottky (Ti/p-Si) and poor Ohmic (Au/p-Si) contact can be modulated into a good Ohmic contact with current density of 18.7 ± 0.6 A/cm(2) and 10.4 ± 0.4 A/cm(2), respectively, showing ~18 and ~30 times improvement. A perfect forward/reverse current ratio of 1.041 is achieved for these low doped p-Si samples.

Room temperature Coulomb blockade effects in Au nanocluster/pentacene single electron transistors.

Single-electron transistors incorporating single ∼1 nm gold nanocluster (AuNCs) and pentacene as a complex charge transport system have been used to study the quantum Coulomb blockade and its single electron tunnelling behaviour at room temperature (RT) (300 K). Monodisperse ultra-small (0.86 ± 0.30 nm) AuNCs were deposited by the tilted-target sputtering technique into 12 nm nanogaps fabricated by high-resolution e-beam lithography. Tunnelling resistance was modulated to ∼10(9) Ω by addition of a pentacene layer, allowing clear observation of quantum staircases and Coulomb oscillations with on/off current modulation ratio of ∼100 in RT current-voltage measurements. The electron addition energy and average quantized energy level spacing were found to be 282 and 80.4 meV, respectively, which are significantly larger than the thermal energy at 300 K (25.9 meV).

Single-Molecule Detection in Nanogap-Embedded Plasmonic Gratings.

We introduce nanogap-embedded silver plasmonic gratings for single-molecule (SM) visualization using an epifluorescence microscope. This silver plasmonic platform was fabricated by a cost-effective nano-imprint lithography technique, using an HD DVD template. DNA/ RNA duplex molecules tagged with Cy3/Cy5 fluorophores were immobilized on SiO2-capped silver gratings. Light was coupled to the gratings at particular wavelengths and incident angles to form surface plasmons. The SM fluorescence intensity of the fluorophores at the nanogaps showed approximately a 100-fold mean enhancement with respect to the fluorophores observed on quartz slides using an epifluorescence microscope. This high level of enhancement was due to the concentration of surface plasmons at the nanogaps. When nanogaps imaged with epifluorescence mode were compared to quartz imaged using total internal reflection fluorescence (TIRF) microscopy, more than a 30-fold mean enhancement was obtained. Due to the SM fluorescence enhancement of plasmonic gratings and the correspondingly high emission intensity, the required laser power can be reduced, resulting in a prolonged detection time prior to photobleaching. This simple platform was able to perform SM studies with a low-cost epifluorescence apparatus, instead of the more expensive TIRF or confocal microscopes, which would enable SM analysis to take place in most scientific laboratories.

Experimental characterization of optical nonlocality in metal-dielectric multilayer metamaterials.

The optical nonlocality in metal-dielectric multilayer metamaterials is characterized experimentally as a function of the angle of incidence with respect to the TE-polarized incident light. The physical mechanism of the difference between the nonlocal effective permittivity and the effective-medium-theory-based effective permittivity depending on the incident angle is theoretically revealed through the analysis of the band structure, the dispersion relation, and the iso-frequency contours according to the transfer-matrix method. Such effective permittivity difference is also retrieved in the metal-dielectric multilayers based on the measured transmission and reflection spectra.

Coatings and surface modifications imparting antimicrobial activity to orthopedic implants.

Bacterial colonization and biofilm formation on an orthopedic implant surface is one of the worst possible outcomes of orthopedic intervention in terms of both patient prognosis and healthcare costs. Making the problem even more vexing is the fact that infections are often caused by events beyond the control of the operating surgeon and may manifest weeks to months after the initial surgery. Herein, we review the costs and consequences of implant infection as well as the methods of prevention and management. In particular, we focus on coatings and other forms of implant surface modification in a manner that imparts some antimicrobial benefit to the implant device. Such coatings can be classified generally based on their mode of action: surface adhesion prevention, bactericidal, antimicrobial-eluting, osseointegration promotion, and combinations of the above. Despite several advances in the efficacy of these antimicrobial methods, a remaining major challenge is ensuring retention of the antimicrobial activity over a period of months to years postoperation, an issue that has so far been inadequately addressed. Finally, we provide an overview of additional figures of merit that will determine whether a given antimicrobial surface modification warrants adoption for clinical use.