Dielectric and Mechanical Properties of 3D Printed Nanocomposites with Varied Particle Diameter.

3D printed nanocomposites provide a method for generating high-performance radio frequency devices. Limited work has been done to investigate the influence the nanoparticle diameter has on the performance of 3D printable nanocomposites. We describe here the development of a family of 3D printable nanocomposite inks formulated from nanoparticles with diameters ranging from 30 to 300 nm. Relative permittivity values for the printed nanocomposites were unaffected by nanoparticle diameter whereas loss tangent, glass transition temperature, and elastic modulus were altered. This work provides a framework for designing 3D printable nanocomposites and highlights the importance that nanoparticle diameter plays in formulation strategy.

Solubilization of Hydrophobic Catalysts Using Nanoparticle Hosts.

A modular strategy for the solubilization and protection of hydrophobic transition metal catalysts using the hydrophobic pockets of water soluble gold nanoparticles is reported. Besides preserving original catalyst activity, this encapsulation strategy provides a protective environment for the hydrophobic catalyst and brings reusability. This system provides a versatile platform for the encapsulation of different hydrophobic transition metal catalysts, allowing a wide range of catalysis in water while uniting the advantages of homogeneous and heterogeneous catalysis in the same system.

Enhanced Laser Desorption/Ionization Mass Spectrometric Detection of Biomolecules Using Gold Nanoparticles, Matrix, and the Coffee Ring Effect.

Nanomaterials have been extensively used as alternate matrices to minimize the low molecular weight interferences observed in typical MALDI but such nanomaterials typically do not improve the spot-to-spot variability that is commonly seen. In this work, we demonstrate that nanoparticles and low matrix concentrations (<2.5 mg/mL) can be used to homogeneously concentrate analytes into a narrow ring by taking advantage of the "coffee ring" effect. Concentration of the samples in this way leads to enhanced signals when compared to conventional MALDI, with higher m/z analytes being enhanced to the greatest extent. Moreover, the ionization suppression often observed in samples with high salt concentrations can be overcome by preparing samples in this way. The ring that is formed is readily visible, allowing the laser to be focused only on spots that contain analyte. The coffee-ring effect represents a new mode by which nanomaterials can be used to enhance the MALDI-based detection of biomolecules.

Holographic aperture ladar with range compression.

Simultaneous range compression and aperture synthesis is experimentally demonstrated with a stepped linear frequency modulated waveform and holographic aperture ladar. The resultant three-dimensional (3D) data has high resolution in the aperture synthesis dimension and is recorded using a conventional low bandwidth focal plane array. Individual cross-range field segments are coherently combined using data driven registration and phase correction methods allowing range compression to be performed without the benefit of a coherent waveform. Furthermore, we demonstrate a synergistically enhanced ability to discriminate image objects due to the coaction of range compression and aperture synthesis. We show that two objects can be precisely located in 3D space, despite being unresolved in two directions, due to resolution gains in both the range and azimuth cross-range dimensions.

Phase gradient algorithm method for three-dimensional holographic ladar imaging.

Three-dimensional (3D) holographic ladar uses digital holography with frequency diversity to add the ability to resolve targets in range. A key challenge is that since individual frequency samples are not recorded simultaneously, differential phase aberrations may exist between them, making it difficult to achieve range compression. We describe steps specific to this modality so that phase gradient algorithms (PGA) can be applied to 3D holographic ladar data for phase corrections across multiple temporal frequency samples. Substantial improvement of range compression is demonstrated with a laboratory experiment where our modified PGA technique is applied. Additionally, the PGA estimator is demonstrated to be efficient for this application, and the maximum entropy saturation behavior of the estimator is analytically described.

Enhanced Laser Desorption/Ionization Mass Spectrometric Detection of Gold Nanoparticles in Biological Samples Using the Synergy between Added Matrix and the Gold Core.

Laser desorption/ionization mass spectrometry (LDI-MS) has been used to detect gold nanoparticles (AuNPs) in biological samples, such as cells and tissues, by ionizing their attached monolayer ligands. Many NP-attached ligands, however, are difficult to ionize by LDI, making it impossible to track these NPs in biological samples. In this work, we demonstrate that concentrations of matrix-assisted LDI (MALDI) matrices an order of magnitude below the values typically used in MALDI can facilitate the selective detection of AuNPs with these ligands, even in samples as complex as cell lysate. This enhanced sensitivity arises from a synergistic relationship between the gold core and the matrix that helps to selectively ionize ligands attached to the AuNPs.

Hybrid organic-inorganic colloidal composite 'sponges' via internal crosslinking.

An effective method for the generation of hybrid organic-inorganic nanocomposite microparticles featuring controlled size and high structural stability is presented. In this process, an oil-in-water Pickering emulsion is formed using hydrophilic amine-functionalized silica nanoparticles. Covalent modification using a hydrophobic maleic anhydride copolymer then alters nanoparticle wettability during crosslinking, causing a core-shell to nanocomposite structural reorganization of the assemblies. The resulting porous nanocomposites maintain discrete microparticle structures and retain payloads in their oil phase even when incubated in competitive solvents such as ethanol.

Co-delivery of protein and small molecule therapeutics using nanoparticle-stabilized nanocapsules.

Combination therapy employing proteins and small molecules provides access to synergistic treatment strategies. Co-delivery of these two payloads is challenging due to the divergent physicochemical properties of small molecule and protein cargos. Nanoparticle-stabilized nanocapsules (NPSCs) are promising for combination treatment strategies since they have the potential to deliver small molecule drugs and proteins simultaneously into the cytosol. In this study, we loaded paclitaxel into the hydrophobic core of the NPSC and self-assembled caspase-3 and nanoparticles on the capsule surface. The resulting combination NPSCs showed higher cytotoxicity than either of the single agent NPSCs, with synergistic action established using combination index values.

Regulating exocytosis of nanoparticles via host-guest chemistry.

Prolonged retention of internalized nanoparticulate systems inside cells improves their efficacy in imaging, drug delivery, and theranostic applications. Especially, regulating exocytosis of the nanoparticles is a key factor in the fabrication of effective nanocarriers for chemotherapeutic treatments but orthogonal control of exocytosis in the cellular environment is a major challenge. Herein, we present the first example of regulating exocytosis of gold nanoparticles (AuNPs), a model drug carrier, by using a simple host-guest supramolecular system. AuNPs featuring quaternary amine head groups were internalized into the cells through endocytosis. Subsequent in situ treatment of a complementary cucurbit[7]uril (CB[7]) to the amine head groups resulted in the AuNP-CB[7] complexation inside cells, rendering particle assembly. This complexation induced larger particle assemblies that remained sequestered in the endosomes, inhibiting exocytosis of the particles without any observed cytotoxicity.

Direct cytosolic delivery of siRNA using nanoparticle-stabilized nanocapsules.

The use of nanoparticle-stabilized nanocapsules (NPSCs) for the direct cytosolic delivery of siRNA is reported. In this approach, siRNA is complexed with cationic arginine-functionalized gold nanoparticles by electrostatic interactions, with the resulting ensemble self-assembled onto the surface of fatty acid nanodroplets to form a NPSC/siRNA nanocomplex. The complex rapidly delivers siRNA into the cytosol through membrane fusion, a mechanism supported by cellular uptake studies. Using destabilized green fluorescent protein (deGFP) as a target, 90% knockdown was observed in HEK293 cells. Moreover, the delivery of siRNA targeting polo-like kinase 1 (siPLK1) efficiently silenced PLK1 expression in cancer cells with concomitant cytotoxicity.

Immobilization and stabilization of lipase (CaLB) through hierarchical interfacial assembly.

Nanostructure-enabled hierarchical assembly holds promise for efficient biocatalyst immobilization for improved stability in bioprocessing. In this work we demonstrate the use of a hierarchical assembly immobilization strategy to enhance the physicochemical properties and stability of lipase B from Candida antarctica (CaLB). CaLB was complexed with iron oxide nanoparticles followed by interfacial assembly at the surface of an oil-in-water emulsion. Subsequent ring opening polymerization of the oil provided cross-linked microparticles that displayed an increase in catalytic efficiency when compared to the native enzyme and Novozym 435. The hierarchical immobilized enzyme assembly showed no leakage from the support in 50% acetonitrile and could be magnetically recovered across five cycles. Immobilized lipase exhibited enhanced thermal and pH stability, providing 72% activity retention after 24 h at 50 °C (pH 7.0) and 62% activity retention after 24 h at pH 3.0 (30 °C); conditions resulting in complete deactivation of the native lipase.

3D Printing of Composite Radiation Shielding for Broad Spectrum Protection of Electronic Systems.

The miniaturization of satellite systems has compounded the need to protect microelectronic components from damaging radiation. Current approaches to mitigate this damage, such as indiscriminate mass shielding, built-in redundancies, and radiation-hardened electronics, introduce high size, weight, power, and cost penalties that impact the overall performance of the satellite or launch opportunities. Additive manufacturing provides an appealing strategy to deposit radiation shielding only on susceptible components within an electronic assembly. Here, a versatile material platform and process to conformally print customized composite inks at room temperature directly and selectively onto commercial-off-the-shelf electronics is described. The suite of inks uses a flexible styrene-isoprene-styrene block copolymer binder that can be filled with particles of different atomic densities for diverging radiation shielding capabilities. Additionally, the system enables the combination of multiple distinct particle species within the same printed structure. The method can produce graded shielding that offers improved radiation attenuation by tailoring both shield geometry and composition to provide comprehensive protection from a broad range of radiation species. The authors anticipate this alternative to traditional shielding methods will enable the rapid proliferation of the next generation of compact satellite designs.

Additive Manufacturing of Multimaterial Composites for Radiation Shielding and Thermal Management.

The harsh radiation environment of space induces the degradation and malfunctioning of electronic systems. Current approaches for protecting these microelectronic devices are generally limited to attenuating a single type of radiation or require only selecting components that have undergone the intensive and expensive process to be radiation-hardened by design. Herein, we describe an alternative fabrication strategy to manufacture multimaterial radiation shielding via direct ink writing of custom tungsten and boron nitride composites. The additively manufactured shields were shown to be capable of attenuating multiple species of radiation by tailoring the composition and architecture of the printed composite materials. The shear-induced alignment during the printing process of the anisotropic boron nitride flakes provided a facile method for introducing favorable thermal management characteristics to the shields. This generalized method offers a promising approach for protecting commercially available microelectronic systems from radiation damage and we anticipate this will vastly enhance the capabilities of future satellites and space systems.

Saturated semiconductor optical amplifier phase modulation for long range laser radar applications.

We investigate the use of a semiconductor optical amplifier operated in the saturation regime as a phase modulator for long range laser radar applications. The nature of the phase and amplitude modulation resulting from a high peak power Gaussian pulse, and the impact this has on the ideal pulse response of a laser radar system, is explored. We also present results of a proof-of-concept laboratory demonstration using phase-modulated pulses to interrogate a stationary target.

Demonstrated resolution enhancement capability of a stripmap holographic aperture ladar system.

Holographic aperture ladar (HAL) is a variant of synthetic aperture ladar (SAL). The two processes are related in that they both seek to increase cross-range (i.e., the direction of the receiver translation) image resolution through the synthesis of a large effective aperture. This is in turn achieved via the translation of a receiver aperture and the subsequent coherent phasing and correlation of multiple received signals. However, while SAL imaging incorporates a translating point detector, HAL takes advantage of a two-dimensional translating sensor array. For the research presented in this article, a side-looking stripmap HAL geometry was used to sequentially image a set of Ronchi ruling targets. Prior to this, theoretical calculations were performed to determine the baseline, single subaperture resolution of our experimental, laboratory-based system. Theoretical calculations were also performed to determine the ideal modulation transfer function (MTF) and expected cross-range HAL image sharpening ratio corresponding to the geometry of our apparatus. To verify our expectations, we first sequentially captured an oversampled collection of pupil plane field segments for each Ronchi ruling. A HAL processing algorithm incorporating a high-precision speckle field registration process was then employed to phase-correct and reposition the field segments. Relative interframe piston phase errors were also removed prior to final synthetic image formation. By then taking the Fourier transform of the synthetic image intensity and examining the fundamental spatial frequency content, we were able to produce experimental modulation transfer function curves, which we then compared with our theoretical expectations. Our results show that we are able to achieve nearly diffraction-limited results for image sharpening ratios as high as 6.43.

Beauty is skin deep: a surface monolayer perspective on nanoparticle interactions with cells and bio-macromolecules.

Surface recognition of biosystems is a critical component in the development of novel biosensors and delivery vehicles, and for the therapeutic regulation of biological processes. Monolayer-protected nanoparticles present a highly versatile scaffold for selective interaction with bio-macromolecules and cells. Through the engineering of the monolayer surface, nanoparticles can be tailored for surface recognition of biomolecules and cells. This review highlights recent progress in nanoparticle-bio-macromolecule/cellular interactions, emphasizing the effect of the surface monolayer structure on the interactions with proteins, DNA, and cell surfaces. The extension of these tailored interactions to hybrid nanomaterials, biosensing platforms, and delivery vehicles is also discussed.

Improving mid-frequency contrast in sparse aperture optical imaging systems based upon the Golay-9 array.

Sparse aperture imaging systems are capable of producing high resolution images while maintaining an overall light collection area that is small compared to a fully filled aperture yielding the same resolution. This is advantageous for applications where size, volume, weight and/or cost are important considerations. However, conventional sparse aperture systems pay the penalty of reduced contrast at midband spatial frequencies. This paper will focus on increasing the midband contrast of sparse aperture imaging systems based on the Golay-9 array. This is one of a family of two-dimensional arrays we have previously examined due to their compact, non-redundant autocorrelations. The modulation transfer function, or normalized autocorrelation, provides a quantitative measure of both the resolution and contrast of an optical imaging system and, along with an average relative midband contrast metric, will be used to compare perturbations to the standard Golay-9 array. Numerical calculations have been performed to investigate the behavior of a Golay-9 array into which autocorrelation redundancy has been introduced and our results have been experimentally verified. In particular we have demonstrated that by proper choice of sub-aperture diameters the average relative midband contrast can be improved by over 55%.

Periodic, pseudonoise waveforms for multifunction coherent ladar.

We report the use of periodic, pseudonoise waveforms in a multifunction coherent ladar system. We exploit the Doppler sensitivity of these waveforms, as well as agile processing, to enable diverse ladar functions, including high range resolution imaging, macro-Doppler imaging, synthetic aperture ladar, and range-resolved micro-Doppler imaging. We present analytic expressions and simulations demonstrating the utility of pseudonoise waveforms for each of the ladar modes. We also discuss a laboratory pseudonoise ladar system that was developed to demonstrate range compression and range-resolved micro-Doppler imaging, as well as the phase recovery common to each of the coherent modes.

Experimental demonstration of a stripmap holographic aperture ladar system.

By synthesizing large effective apertures through the translation of a smaller imaging sensor and the subsequent proper phasing and correlation of detected signals in postprocessing, holographic aperture ladar (HAL) systems seek to increase the resolution of remotely imaged targets. The stripmap HAL process was demonstrated in the laboratory, for the first time to our knowledge. Our results show that the stripmap HAL transformation can precisely account for off-axis transmitter induced phase migrations. This in turn allows multiple pupil plane field segments, sequentially collected across a synthetic aperture, to be coherently mosaiced together. As a direct consequence, we have been able to confirm the capability of the HAL method to potentially provide substantial increases in longitudinal cross-range resolution. The measurement and sampling of complex pupil plane field segments, as well as target related issues arising from short laboratory ranges, have also been addressed.

Monte Carlo simulation of multiple photon scattering in sugar maple tree canopies.

Detecting objects hidden beneath forest canopies is a difficult task for optical remote sensing systems. Rather than relying upon the existence of gaps between leaves, as other researchers have done, our ultimate goal is to use light scattered by leaves to image through dense foliage. Herein we describe the development of a Monte Carlo model for simulating the scattering of light as it propagates through the leaves of an extended tree canopy. We measured several parameters, including the gap fraction and maximum leaf-area density, of a nearby sugar maple tree grove and applied them to our model. We report the results of our simulation in both the ground and the receiver planes for an assumed illumination angle of 80 degrees. To validate our model, we then illuminated the sugar maple tree grove at 80 degrees and collected data both on the canopy floor and at our monostatic receiver aperture. Experimental results were found to correlate well with our simulated expectations.