Liquid-core polymer nanocapsules prepared using flash nanoprecipitation.

Hypothesis: Nanocapsules, consisting of a solid shell and a liquid core, are an interesting class of materials with numerous applications and various methods of synthesis. One common method for synthesis of nanoparticles is flash nanoprecipitation. For a multicomponent system consisting of a liquid (n-hexadecane) and solid (polystyrene), we hypothesize that nanocapsules will form from droplets created by the turbulent mixing in the nanoprecipitation process. We anticipate n-hexadecane molecules should phase-separate more rapidly from the non-solvent, thus becoming the core, while the more slowly diffusing polystyrene forms the shell. Additionally, we predict that the amount of both n-hexadecane and polystyrene used in creating these nanocapsules will influence capsule size. Experiments: Using flash nanoprecipitation, we synthesized nanocapsules of a polystyrene shell and liquid core of n-hexadecane. We varied the concentrations of both polystyrene and n-hexadecane and characterized the resulting dispersions using dynamic light scattering and scanning electron microscopy. Findings: Our experiments demonstrate that flash nanoprecipitation can be employed to create nanocapsules with radii ranging from 50 to 200 nm, with radii of the n-hexadecane cores between 35 and 175 nm and polystyrene shells with thickness ranging from 7 to 62 nm. We used various methods of analysis to confirm this core/shell morphology and applied a droplet model to explain the dependence of particle size on initial concentrations of n-hexadecane and polystyrene.

Observation of Multi-Phonon Emission in Monolayer WS2 on Various Substrates.

Transition metal dichalcogenides (TMDs) have unique absorption and emission properties that stem from their large excitonic binding energies, reduced-dielectric screening, and strong spin-orbit coupling. However, the role of substrates, phonons, and material defects in the excitonic scattering processes remains elusive. In tungsten-based TMDs, it is known that the excitons formed from electrons in the lower-energy conduction bands are dark in nature, whereas low-energy emissions in the photoluminescence spectrum have been linked to the brightening of these transitions, either via defect scattering or via phonon scattering with first-order phonon replicas. Through temperature and incident-power-dependent studies of WS2 grown by CVD or exfoliated from high-purity bulk crystal on different substrates, we demonstrate that the strong exciton-phonon coupling yields brightening of dark transitions up to sixth-order phonon replicas. We discuss the critical role of defects in the brightening pathways of dark excitons and their phonon replicas, and we elucidate that these emissions are intrinsic to the material and independent of substrate, encapsulation, growth method, and transfer approach.

Molecular Parameters Promoting High Relaxivity in Cluster-Nanocarrier Magnetic Resonance Imaging Contrast Agents.

We have investigated the mechanism of relaxivity for two magnetic resonance imaging contrast agents that both employ a cluster-nanocarrier design. The first system termed Mn8Fe4-coPS comprises the cluster Mn8Fe4O12(L)16(H2O)4 or Mn8Fe4 (1) (L = carboxylate) co-polymerized with polystyrene to form ∼75 nm nanobeads. The second system termed Mn3Bpy-PAm used the cluster Mn3(O2CCH3)6(Bpy)2 or Mn3Bpy (2) where Bpy = 2,2'-bipyridine, entrapped in ∼180 nm polyacrylamide nanobeads. Here, we investigate the rate of water exchange of the two clusters, and corresponding cluster-nanocarriers, in order to elucidate the mechanism of relaxivity in the cluster-nanocarrier. Swift-Connick analysis of O-17 NMR was used to determine the water exchange rates of the clusters and cluster-nanocarriers. We found distinct differences in the water exchange rate between Mn8Fe4 and Mn8Fe4-coPS, and we utilized these differences to elucidate the nanobead structure. Using the transverse relaxivity from O-17 NMR line widths, we were able to determine the hydration state of the Mn3Bpy (2) cluster as well as Mn3Bpy-PAm. Using these hydration states in the Swift-Connick analysis of O-17 NMR, we found the water exchange rate to be extremely close in value for the cluster Mn3Bpy and cluster-nanocarrier Mn3Bpy-PAm.

Particle Formation Mechanisms in the Nanoprecipitation of Polystyrene.

Numerous precipitation methods for creating nanoparticle dispersions that are based on mixing a solution with a miscible nonsolvent have been developed. Here, we show that for polymer particles, the formation is highly dependent on the rate of mixing. We also demonstrate the importance of the glass transition of the polymers on particle formation. A simple model of droplet formation during mixing provides a satisfactory description of the observed dependence of particle size on polymer molecular weight, concentration, solvent ratio, and mixing conditions.

Targeting of intragraft reactive oxygen species by APP-103, a novel polymer product, mitigates ischemia/reperfusion injury and promotes the survival of renal transplants.

Inflammatory responses associated with ischemia/reperfusion injury (IRI) play a central role in alloimmunity and transplant outcomes. A key event driving these inflammatory responses is the burst of reactive oxygen species (ROS), with hydrogen peroxide (H2 O2 ) as the most abundant form that occurs as a result of surgical implantation of the donor organ. Here, we used a syngeneic rat renal transplant and IRI model to evaluate the therapeutic properties of APP-103, a polyoxalate-based copolymer molecule containing vanillyl alcohol (VA) that exhibits high sensitivity and specificity toward the production of H2 O2 . We show that APP-103 is safe, and that it effectively promotes kidney function following IRI and survival of renal transplants. APP-103 reduces tissue injury and IRI-associated inflammatory responses in models of both warm ischemia (kidney clamping) and prolonged cold ischemia (syngeneic renal transplant). Mechanistically, we demonstrate that APP-103 exerts protective effects by specifically targeting the production of ROS. Our data introduce APP-103 as a novel, nontoxic, and site-activating therapeutic approach that effectively ameliorates the consequences of IRI in solid organ transplantation.

Paramagnetic Clusters of Mn3(O2CCH3)6(Bpy)2 in Polyacrylamide Nanobeads as a New Design Approach to a T1- T2 Multimodal Magnetic Resonance Imaging Contrast Agent.

There is an increasing need for gadolinium-free magnetic resonance imaging (MRI) contrast agents, particularly for patients suffering from chronic kidney disease. Using a cluster-nanocarrier combination, we have identified a novel approach to the design of biomedical nanomaterials and report here the criteria for the cluster and the nanocarrier and the advantages of this combination. We have investigated the relaxivity of the following manganese oxo clusters: the parent cluster Mn3(O2CCH3)6(Bpy)2 (1) where Bpy = 2,2'-bipyridine and three new analogs, Mn3(O2CC6H4CH═CH2)6(Bpy)2 (2), Mn3(O2CC(CH3)═CH2)6(Bpy)2 (3), and Mn3O(O2CCH3)6(Pyr)2 (4) where Pyr = pyridine. The parent cluster, Mn3(O2CCH3)6(Bpy)2 (1), had impressive relaxivity ( r1 = 6.9 mM-1 s-1, r2 = 125 mM-1 s-1) and was found to be the most amenable for the synthesis of cluster-nanocarrier nanobeads. Using the inverse miniemulsion polymerization technique (1) in combination with the hydrophilic monomer acrylamide, we synthesized nanobeads (∼125 nm diameter) with homogeneously dispersed clusters within the polyacrylamide matrix (termed Mn3Bpy-PAm). The nanobeads were surface-modified by co-polymerization with an amine-functionalized monomer. This enabled various postsynthetic modifications, for example, to attach a near-IR dye, Cyanine7, as well as a targeting agent. When evaluated as a potential multimodal MRI contrast agent, high relaxivity and contrast were observed with r1 = 54.4 mM-1 s-1 and r2 = 144 mM-1 s-1, surpassing T1 relaxivity of clinically used Gd-DTPA chelates as well as comparable T2 relaxivity to iron oxide microspheres. Physicochemical properties, cellular uptake, and impacts on cell viability were also investigated.

Ambient effects on photogating in MoS2 photodetectors.

Atomically thin transition metal dichalcogenides (TMDs) are ideal candidates for ultrathin optoelectronics that are flexible and semitransparent. Photodetectors based on TMDs show remarkable performance, with responsivity and detectivity higher than 103 AW-1 and 1012 Jones, respectively, but they are plagued by response times as slow as several tens of seconds. Although it is well established that gas adsorbates such as water and oxygen create charge traps and significantly increase both the responsivity and the response time, the underlying mechanism is still unclear. Here we study the influence of adsorbates on MoS2 photodetectors under ambient conditions, vacuum and illumination at different wavelengths. We show that, for wavelengths sufficiently short to excite electron-hole pairs in the MoS2, light illumination causes desorption of water and oxygen molecules. The change in the molecular gating provided by the physisorbed molecules is the dominant contribution to the device photoresponse in ambient conditions.

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates.

Organic ligands with carboxylate functionalities have been shown to affect the solubility, speciation, and overall chemical behavior of tetravalent metal ions. While many reports have focused on actinide complexation by relatively simple monocarboxylates such as amino acids, in this work we examined Th(IV) and U(IV) complexation by 4-hydroxybenzoic acid in water with the aim of understanding the impact that the organic backbone has on the solution and solid state structural chemistry of thorium(IV) and uranium(IV) complexes. Two compounds of the general formula [An6O4(OH)4(H2O)6(4-HB)12]· nH2O [An = Th (Th-1) and U (U-1); 4-HB = 4-hydroxybenzoate] were synthesized via room-temperature reactions of AnCl4 and 4-hydroxybenzoic acid in water. Solid state structures were determined by single-crystal X-ray diffraction, and the compounds were further characterized by Raman, infrared, and optical spectroscopies and thermogravimetry. The magnetism of U-1 was also examined. The structures of the Th and U compounds are isomorphous and are built from ligand-decorated oxo/hydroxo-bridged hexanuclear units. The relationship between the building units observed in the solid state structure of U-1 and those that exist in solution prior to crystallization as well as upon dissolution of U-1 in nonaqueous solvents was investigated using small-angle X-ray scattering, ultraviolet-visible optical spectroscopy, and dynamic light scattering. The evolution of U solution speciation as a function of reaction time and temperature was examined. Such effects as well as the impact of the ligand on the formation and evolution of hexanuclear U(IV) clusters to UO2 nanoparticles compared to prior reported monocarboxylate ligand systems are discussed. Unlike prior reported syntheses of Th and U(IV) hexamers where the pH was adjusted to ∼2 and 3, respectively, to drive hydrolysis, hexamer formation with the HB ligand appears to be promoted only by the ligand.

Highly photoresponsive, ZnO nanorod-based photodetector for operation in the visible spectral range.

While significant advances have been made for gold nanoparticle (AuNP)-coupled zinc oxide (ZnO) as visibly blind, ultraviolet photodetection devices, very few ZnO nanomaterial systems have been developed specifically for use in the visible wavelength regime. Further efforts to develop ZnO-based visible photodetectors (PDs) are still highly warranted in order to better understand the precise effect of AuNP load, operation wavelength, and beam position on the device output. In this study, we demonstrate significantly enhanced, photoresponse behaviors of AuNP-coupled ZnO nanorod (NR) network devices in the visible wavelength range with their photoresponse capacity comparable to, if not far exceeding, most commercial PDs as well as recently reported, visible, AuNP-coupled ZnO detectors. In addition, the nature and degree of the photoresponsivity enhancement are systematically elucidated by investigating their light-triggered electrical signals under varying incident wavelengths, AuNP amounts, and illumination positions. We discuss a possible photoconduction mechanism of our AuNP-coupled ZnO NR PDs and the origins of the high photoresponsivity. Specifically related to the AuNP amount-dependent photoresponse behaviors, the nanoparticle density yielding photoresponse maxima is explained as the interplay between localized surface plasmon resonance, plasmonic heating, and scattering in our photothermoelectric effect-driven device. We show that the AuNP-coupled ZnO NR PDs can be constructed via a straightforward method without the need for ultrahigh vacuum, sputtering procedures, or photo/electron-beam lithographic tools. Hence, the approach demonstrated in this study may serve as a convenient and viable means to advance the current state of ZnO-based PDs for operation in the visible spectral range with greatly increased photoresponsivity.

Indium Tin Oxide Nanowire Networks as Effective UV/Vis Photodetection Platforms.

We demonstrate that indium tin oxide nanowires (ITO NWs) and cationic polymer-modified ITO NWs configured in a network format can be used as high performing UV/vis photodetectors. The photovoltage response of ITO NWs is much higher than similarly constructed devices made from tin oxide, zinc tin oxide, and zinc oxide nanostructures. The ITO NW mesh-based devices exhibit a substantial photovoltage (31-100 mV under illumination with a 1.14 mW 543 nm laser) and photocurrent (225-325 µA at 3 V). The response time of the devices is fast with a rise time of 20-30 µs and a decay time of 1.5-3.7 ms when probed with a 355 nm pulsed laser. The photoresponsivity of the ITO NW devices ranges from 0.07 to 0.2 A/W at a 3 V bias, whose values are in the performance range of most commercial UV/vis photodetectors. Such useful photodetector characteristics from our ITO NW mesh devices are attained straightforwardly without the need for complicated fabrication procedures involving highly specialized lithographic tools. Therefore, our approach of ITO NW network-based photodetectors can serve as a convenient alternative to commercial or single NW-based devices.

The effects of particle shape and size on T2 relaxation in magnetic resonance imaging.

Superparamagnetic iron oxide nanoparticles have recently been developed as T2 contrast agents for magnetic resonance imaging. Here we report the dependence of the phase relaxivity, r2, on the particle shape. We show that the size dependence of the relaxivity for spherical particles can be generalized to spheroidal particles. In addition, we show that the saturation of relaxivity above a certain size observed in spherical particles does not occur in the spheroidal particles investigated.

Magnetic nanobeads as potential contrast agents for magnetic resonance imaging.

Metal-oxo clusters have been used as building blocks to form hybrid nanomaterials and evaluated as potential MRI contrast agents. We have synthesized a biocompatible copolymer based on a water stable, nontoxic, mixed-metal-oxo cluster, Mn8Fe4O12(L)16(H2O)4, where L is acetate or vinyl benzoic acid, and styrene. The cluster alone was screened by NMR for relaxivity and was found to be a promising T2 contrast agent, with r1 = 2.3 mM(-1) s(-1) and r2 = 29.5 mM(-1) s(-1). Initial cell studies on two human prostate cancer cell lines, DU-145 and LNCap, reveal that the cluster has low cytotoxicity and may be potentially used in vivo. The metal-oxo cluster Mn8Fe4(VBA)16 (VBA = vinyl benzoic acid) can be copolymerized with styrene under miniemulsion conditions. Miniemulsion allows for the formation of nanometer-sized paramagnetic beads (~80 nm diameter), which were also evaluated as a contrast agent for MRI. These highly monodispersed, hybrid nanoparticles have enhanced properties, with the option for surface functionalization, making them a promising tool for biomedicine. Interestingly, both relaxivity measurements and MRI studies show that embedding the Mn8Fe4 core within a polymer matrix decreases r2 effects with little effect on r1, resulting in a positive T1 contrast enhancement.

Coalescence of single photons emitted by disparate single-photon sources: the example of InAs quantum dots and parametric down-conversion sources.

Single photons produced by fundamentally dissimilar physical processes will in general not be indistinguishable. We show how photons produced from a quantum dot and by parametric down-conversion in a nonlinear crystal can be manipulated to be indistinguishable. The measured two-photon coalescence probability is 16%, and is limited by quantum-dot decoherence. Temporal filtering to the quantum-dot coherence time and accounting for detector time response increases this to 61% while retaining 25% of the events. This technique can connect different elements in a scalable quantum network.

Miniemulsion synthesis of metal-oxo cluster containing copolymer nanobeads.

Hybrid nanobeads containing either a manganese-oxo or manganese-iron-oxo cluster have been prepared via the miniemulsion polymerization technique. Two new ligand substituted oxo clusters, Mn(12)O(12)(VBA)(16)(H(2)O)(4) and Mn(8)Fe(4)O(12)(VBA)(16)(H(2)O)(4) (where VBA = 4-vinylbenzoate), have been prepared and characterized. Polymerization of the functionalized metal-oxo clusters with styrene under miniemulsion conditions produced monodispersed polymer nanoparticles as small as ~60 nm in diameter. The metal-oxo polymer nanobeads were fully characterized in terms of synthetic parameters, composition, structure, and magnetic properties.

Direct integration of nanoscale conventional and slot waveguides.

Slot waveguides can provide high optical confinement in a nanoscale low-index layer. While a conventional waveguide has a Gaussian-like Eigenmode profile, the Eigenmode profile of a slot waveguide is quite non-Gaussian type, due to the large discontinuity of refractive indices and thus the transverse electric field component between the high and low index layers of a slot waveguide. Although the field profiles of the two types of waveguides seem different, here we show that direct integration of conventional and slot waveguides yields efficient coupling of light into and out of slot waveguides using the rigorous finite-difference time domain method. The proposed direct coupling method has comparable performance to recently proposed taper based coupling methods, while having advantages in easier integration with conventional waveguide optics and higher integration density. We also show that coupling efficiency is not sensitive to the symmetricity of the slot waveguide, resulting in good manufacturing tolerance. The proposed direct coupler may have a number of applications in lightwave interconnects, sensing and data storage.

Surface attached manganese-oxo clusters as potential contrast agents.

Surface attachment of the manganese-oxo cluster known as Mn-12 provided aqueous solution stabilization that allowed investigation of the use of the cluster as an MRI contrast agent.

Endohedral fullerenes for organic photovoltaic devices.

So far, one of the fundamental limitations of organic photovoltaic (OPV) device power conversion efficiencies (PCEs) has been the low voltage output caused by a molecular orbital mismatch between the donor polymer and acceptor molecules. Here, we present a means of addressing the low voltage output by introducing novel trimetallic nitride endohedral fullerenes (TNEFs) as acceptor materials for use in photovoltaic devices. TNEFs were discovered in 1999 by Stevenson et al. ; for the first time derivatives of the TNEF acceptor, Lu(3)N@C(80), are synthesized and integrated into OPV devices. The reduced energy offset of the molecular orbitals of Lu(3)N@C(80) to the donor, poly(3-hexyl)thiophene (P3HT), reduces energy losses in the charge transfer process and increases the open circuit voltage (Voc) to 260 mV above reference devices made with [6,6]-phenyl-C(61)-butyric methyl ester (C(60)-PCBM) acceptor. PCEs >4% have been observed using P3HT as the donor material. This work clears a path towards higher PCEs in OPV devices by demonstrating that high-yield charge separation can occur with OPV systems that have a reduced donor/acceptor lowest unoccupied molecular orbital energy offset.

Right-angle slot waveguide bends with high bending efficiency.

Two right-angle bends for nanoscale slot waveguides with high bending efficiency based on a corner mirror and different resonant cavities are presented, one with a triangular cavity and the other with a square cavity. Through two-dimensional parametric scanning of the position of the mirror and the dimension of the cavity, a maximum bending efficiency calculated using mode overlap integral (MOI) of 94.3% is achieved for the bend with the triangular cavity and 93.1% is achieved for the bend with the square cavity. Although they both have similar bending performance, the position of the mirror is different between the two cases.

Phthalocyanine nanoparticle formation in supersaturated solutions.

Self-organization of molecules in solution is an important natural and synthetic process, in particular for the preparation of nanomaterials. However, the mechanism of growth for solution-based nanoparticle formation is not always well understood. We present results that clarify these mechanisms in solutions of magnesium phthalocyanine in which the self-organization is induced by addition of a miscible nonsolvent. From simultaneous measurements of the sizes of the growing nanoparticles by photon correlation spectroscopy and the molecular concentration by absorption and fluorescence spectroscopy, we have found that the particles do not grow by molecular diffusion to the surfaces. These results suggest the importance of unstable clusters in the growth process. We also observed a strong dependence of the particle size on the initial concentration which we attribute to effects of the curvature of the solubility curve.

A three-dimensional wide-angle BPM for optical waveguide structures.

Algorithms for effective modeling of optical propagation in three- dimensional waveguide structures are critical for the design of photonic devices. We present a three-dimensional (3-D) wide-angle beam propagation method (WA-BPM) using Hoekstra's scheme. A sparse matrix algebraic equation is formed and solved using iterative methods. The applicability, accuracy and effectiveness of our method are demonstrated by applying it to simulations of wide-angle beam propagation, along with a technique for shifting the simulation window to reduce the dimension of the numerical equation and a threshold technique to further ensure its convergence. These techniques can ensure the implementation of iterative methods for waveguide structures by relaxing the convergence problem, which will further enable us to develop higher-order 3-D WA-BPMs based on Padé approximant operators.