Absorption-invariant focusing efficiency for wavefront-shaping controlled reflection from absorbing disordered media.

We numerically model the influence of absorption on wavefront-shaping controlled reflection from absorbing disordered media and provide experimental verification of our model. We find that absorption modifies the reflection eigenvalue density, the average reflectance, and the reflection matrix element density. However, we also find that despite these effects, the efficiency of wavefront-shaping controlled reflection is invariant with absorption.

Burn Chamber Test of Ex Situ Thermal Impulse Sensors.

Recently, we reported on a novel ex situ thermal impulse sensing technique (based on lanthanide-doped oxide precursor nanoparticles) for use in structural fire forensics and demonstrated its functionality in small-scale lab-based tests. As a next step we have now performed a large-scale lab test at the US Bureau of Alcohol, Tobacco, Firearms, and Explosives (ATF) Fire Research Laboratory using a burn chamber with three sand burners. In this test we demonstrate our technique's ability to determine the average temperature experienced by surfaces during the fire. While we successfully demonstrate our techniques accuracy, we also discover several previously unknown vulnerabilities. Namely, we find that: (1) our current method of embedding sensors in paint results in our sensor particles being difficult to recover (due to a large quantity of debris), (2) the current test panels have poor survivability, (3) debris from the fire tests interferes with excitation of dopant Dy ions (limiting our sensors' functionality), and (4) dispersal in paint results in suppression of the (metastable)tetragonal-to-monoclinic phase transition of ZrO2. To overcome these vulnerabilities we are evaluating new panel materials, paints, and lanthanide-dopants.

Nanoscale Ex Situ Thermal Impulse Sensors for Structural Fire Forensics.

We developed nanoscale ex situ thermal impulse (i.e., the temperature and duration of a heating event) sensors for structural fire forensics using a mixture of two lanthanide-doped oxide precursors (precursor Eu:ZrO2 and precursor Dy:Y2O3) that undergo irreversible phase changes when heated. These changes are probed using photoluminescence (PL) spectroscopy with the PL spectra being dependent on the thermal impulse (TI) experienced by the sensors. By correlating the PL spectra to different in-lab TIs, we are able to produce a spectroscopic calibration for our sensors. This calibration allows us to determine an unknown TI of a heating event using only the PL spectrum of the heated TI sensors. In this study, we report on the calibration of these sensors for isothermal heating durations up to 600 s and isothermal temperatures up to 1273 K. Using this calibration, we also demonstrate their ability to determine an unknown TI and demonstrate their functionality when dispersed into paint, which is heated in the presence of drywall.

Initial tamper tests of novel tamper-indicating optical physical unclonable functions.

Optical physical unclonable functions (O-PUFs) are materials containing a large number of randomly distributed degrees of freedom that can be probed optically. We develop tamper-indicating O-PUF seals using polyurethane adhesives with dispersed nanoparticles, where authentication is performed by use of wavefront-shaping controlled reflection. We test the material's and authentication method's tamper-indicating ability using tampering attacks including: mechanical, thermal, and chemical attacks, with the results demonstrating the material/method's robust tamper-indicating ability. Additionally, we demonstrate that authentication depends strongly on the microscopic distribution of nanoparticles within the polymer, which is unfeasibly difficult to clone. These results are the first demonstration of the validity of this technique for use as tamper-indicating seals.

Microgenetic optimization algorithm for optimal wavefront shaping.

One of the main limitations of utilizing optimal wavefront shaping in imaging and authentication applications is the slow speed of the optimization algorithms currently being used. To address this problem we develop a microgenetic optimization algorithm (µGA) for optimal wavefront shaping. We test the abilities of the µGA and make comparisons to previous algorithms (iterative and simple-genetic) by using each algorithm to optimize transmission through an opaque medium. From our experiments we find that the µGA is faster than both the iterative and simple-genetic algorithms and that both genetic algorithms are more resistant to noise and sample decoherence than the iterative algorithm.

Self-healing organic-dye-based random lasers.

One of the primary difficulties in the implementation of organic-dye-based random lasers is the tendency of organic dyes to irreversibly photodecay. In this Letter, we report the observation of "reversible" photodegradation in a Rhodamine 6G and ZrO2 nanoparticle-doped polyurethane random laser. We find that during degradation, the emission broadens, redshifts, and decreases in intensity. After degradation, the system is observed to self-heal leading to the emission returning to its pristine intensity, giving a recovery efficiency of 100%. While the peak intensity fully recovers, the process is not strictly "reversible", as the emission after recovery is still found to be broadened and redshifted. The combination of the peak emission fully recovering and the broadening of the emission leads to a remarkable result: the random laser cycled through degradation, and recovery has a greater integrated emission intensity than the pristine system.

Bimetallic nanostructures as active Raman markers: gold-nanoparticle assembly on 1D and 2D silver nanostructure surfaces.

It is demonstrated that bimetallic silver-gold anisotropic nanostructures can be easily assembled from various nanoparticle building blocks with well-defined geometries by means of electrostatic interactions. One-dimensional (1D) silver nanowires, two-dimensional (2D) silver nanoplates, and spherical gold nanoparticles are used as representative building blocks for bottom-up assembly. The gold nanoparticles are electrostatically bound onto the 1D silver nanowires and the 2D silver nanoplates to give bimetallic nanostructures. The unique feature of the resulting nanostructures is the particle-to-particle interaction that subjects absorbed analytes to an enhanced electromagnetic field with strong polarization dependence. The Raman activity of the bimetallic nanostructures is compared with that of the individual nanoparticle blocks by using rhodamine 6G solution as the model analyte. The Raman intensity of the best-performing silver-gold nanostructure is comparable with the dense array of silver nanowires and silver nanoplates that were prepared by means of the Langmuir-Blodgett technique. An optimized design of a single-nanostructure substrate for surface-enhanced Raman spectroscopy (SERS), based on a wet-assembly technique proposed here, can serve as a compact and low-cost alternative to fabricated nanoparticle arrays.

Formation and optical properties of compression-induced nanoscale buckles on silver nanowires.

An intriguing formation of nanoscale buckles is discovered when an array of aligned silver nanowires was deposited onto prestrained polydimethylsiloxane substrates. The spacing distance between the resulting silver nanoparticles corresponds to the buckling wavelength of the silver nanowires. The buckled nanowires exhibit unique optical properties, such as interruption of scattered polarized photons and emission of photons from subwavelength structure, as well as surface-enhanced Raman scattering at the vicinity of the formed nanobuckles. In this way, they have great potentials for nano-opto devices, catalysts for chemical reactions, and functional materials for chemical detections.

Nanoporous membranes with mixed nanoclusters for Raman-based label-free monitoring of peroxide compounds.

Monitoring trace amounts of peroxide-based molecules is challenging because of the lack of common optical signatures (fluorescence or absorption in UV-vis range) or chemical functionality easily detectable with common routines. To overcome this issue, we suggest a photochemical decomposition approach followed by the analysis of chemical fragments by a fast, sensitive, and reliable Raman spectroscopic method. To facilitate this approach, we employed a novel design of surface-enhanced Raman scattering (SERS)-active nanoporous substrate based on porous alumina membranes decorated with mixed nanoclusters composed of gold nanorods and nanoparticles. The detectable amount of HMTD below 2 pg demonstrated here is about 3 orders of magnitude lower than the current limit of detection. We suggest that laser-induced photocatalytic decomposition onto nanoparticle clusters is critical for achieving label-free detection of unstable and nonresonant organic molecules.

Structure and properties of functionalized bithiophenesilane monodendrons.

This study reports a focal group modification of bithiophenesilane monodendrons and its effect on their molecular ordering in solution, bulk, and surface. We investigated hydrophobic MDn monodendrons and COOH-functionalized MDn-COOH monodendrons with generations, n=0, 1, 2, and 3. We observed that increasing the number of branches led to the progressive blue shift, indicating distorted packing of branched thiophene fragments of MDn. In contrast, MDn-COOH monodendrons showed a progressive red shift with the increasing generation number, indicating gradual domination of sigma-pi interactions. Moreover, the introduction of a focal carboxylic group resulted in the formation of a highly crystalline state for the linear MD0-COOH compound with separated alkyl tail-thiophene packing, which limits pi-pi interactions. Increasing branching in the COOH-containing monodendrons resulted in a hydrophobic-hybrophilic balance sufficient to form stable and uniform Langmuir monolayers at the air-water at a modest surface pressure (<10 mN/m), easily transferrable to a solid substrate. However, a further increase in the thickness of the surface layers from tens to hundreds of nanometers via Langmuir-Blodgett (LB) deposition or spin casting is limited by the formation of globular surface aggregates because of strong intermolecular interactions. A modest red shift observed for condensed Langmuir monolayers indicates densification of thiophene branches and limited intramonolayer crystallization, which preserves photoluminescence. In contrast, thicker surface films showed a significant red shift, confirming a dense molecular packing with strong pi-pi interactions, which results in photoluminescence quenching.

Bulk and surface assembly of branched amphiphilic polyhedral oligomer silsesquioxane compounds.

This study probes the behavior of two series of organic-functionalized core-shell silsesquioxane (POSS-M)p-(x/y) derivatives with various hydrophobic-hydrophilic terminal group compositions in the bulk state and within mono- and multilayered films at the air-water interface and on solid surface. POSS-M refers to mixed silsesquioxane cores, in contrast to the geometrically specific POSS compounds. It is composed of polyhedra, incompletely condensed polyhedra, ladder-type structures, linear structures, and all the possible combinations thereof and attracts great interest because of its facile preparation, low polydispersity, high yield, and low cost. The two series of (POSS-M)p-(x/y) molecules are different in hydrophobic-hydrophilic balance of their terminal groups, with x and y respectively referring to the molar percent of -OCONH-C(18)H(37) tails and -OH for p = 1 and the percent of -OCONH-C(18)H(37) tails and -OCO-C(6)H(4)COOH terminal groups for p = 2. In the bulk state, the presence of aromatic rings in (POSS-M)2-(x/y) series resulted in a lower symmetry crystal structure than the (POSS-M)1-(x/y) series. Moreover, the (POSS-M)p-(x/y) molecules that contain a sufficient amount of -OCONH-C(18)H(37) tails exhibit double endothermic transition, which attributed to the melting of alkyl chains followed by the melting of the unit cells of (POSS-M) cores. The surface morphologies for the various hydrophobic-hydrophilic combinations at surface pressure p = 0.5 mN/m are similar to that observed for the classical amphiphilic star polymers. However, at higher surface pressure (p > or = 5 mN/m), the POSS-M compounds with lower content of hydrophilic groups form a uniform monolayer.

Toroid morphology by ABC-type amphiphilic rod-coil molecules at the air-water interface.

The interfacial and aggregation behavior of the ABC-type amphiphilic molecules with semirigid dumbbell-shaped core and variable length of hydrophobic branched tails (R=(CH2)nCH3 with n=5 (1), 9 (2), 13 (3)) were investigated. At low surface pressure, smooth, uniform monolayers were formed at the air-water interface by molecules 1 and 2, whereas for molecule 3 unique 2D toroid aggregates have been formed. These aggregates were relatively stable within a range of surface pressure and spreading solution concentration. Upon compression, the 2D toroid aggregates collapsed into large, round 3D aggregates. Finally, the choice of spreading solvent has a great influence on aggregation formation into 2D or 3D micelles as a result of the variable balance of the hydrophobic interactions of branched tails and the pi-pi stacking interaction between aromatic segments.

Molecular reorganization of paired assemblies of T-shaped rod-coil amphiphilic molecule at the air-water interface.

A T-shaped aromatic amphiphilic molecule based on linear oligo(ethylene oxide) was synthesized. We suggest that its peculiar interfacial behavior at the air-water interface and the structure of the Langmuir-Blodgett monolayer are associated with its peculiar T-shape and competing steric and amphiphilic interactions at different surface pressures. At low surface pressure, uniform and smooth monolayers were formed. Upon compression, the molecular reorganization from spherical to cylindrical transformation occurred, as caused by the submerging of the oligo(ethylene oxide) chains, providing for efficient pi-pi interactions of the central core. At the highest surface pressure, the monolayer collapses into bilayer domains, following a bicontinuous network formation which tends to transform into a perforated film. The unique shape of T-like rigid aromatic cores makes their structural reorganization very peculiar with paired, dimerlike molecular packing dominating in gas and solid states. This paired aggregation is so strong that it is preserved in the course of flipping and formation of vertically oriented backbones.

Surface morphologies of Langmuir-Blodgett monolayers of PEOnPSn multiarm star copolymers.

Star polymers composed of equal numbers of poly(ethylene oxide) (PEO) and polystyrene (PS) arms with variable lengths and a large (up to 38 total) number of arms, PEO(n)PS(n), have been examined for their ability to form domain nanostructures at the air-water and air-solid interfaces. All PEO(n)PS(n) star polymers formed stable Langmuir-Blodgett (LB) monolayers transferable to a solid substrate. A range of nanoscale surface morphologies have been observed, ranging from cylindrical to circular domains to bicontinuous structures as the weight fraction of the PEO block varied from 19% to 88% and n from 8 to 19. For the PS-rich stars and at elevated surface pressure, a two-dimensional supramolecular netlike nanostructure was formed. In contrast, in the PEO-rich star polymer with the highest PEO content, we observed peculiar dendritic superstructures caused by intramolecular segregation of nonspherical core-shell micellar structures. On the basis of Langmuir isotherms and observed monolayer morphologies, three different models of possible surface behavior of the star polymers at the interfaces were proposed.