VTechWorks Repository :: Browsing by Author "Robinson, Hans D."

Browsing by Author "Robinson, Hans D."

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Adaptive Control of Waveguide Modes in Two-Mode Fibers
Lu, Peng (Virginia Tech, 2016-04-04)
Few mode fibers and multimode fibers (MMFs) are traditionally regarded as unsuitable for important applications such as communications and sensing. A major challenge in using MMFs for aforementioned applications is how to precisely control the waveguide modes propagating within MMFs. In this thesis, we experimentally demonstrate a generic method for controlling the linearly polarized (LP) modes within a two-mode fiber (TMF). Our method is based on adaptive optics (AO), where one utilizes proper feedback signals to shape the wavefront of the input beam in order to achieve the desired LP mode composition. In the first part of this thesis, we demonstrate the feasibility of AO-based mode control by using the correlation between the experimentally measured field distribution and the desired mode profiles as feedback for wavefront optimization. Selectively excitation of pure LP modes or their combinations at the distal end of a TMF are shown. Furthermore, we demonstrate that selective mode excitation in the TMF can be achieved by using only 5×5 independent phase blocks. Afterwards, we extend our AO-based mode control method to more practical scenarios, where feedback signals are provided by all-fiber devices such as a directional fiber coupler or fiber Bragg gratings (FBGs). Using the coupling ratio of a directional coupler as feedback, we demonstrate adaptive control of LP modes at the two output ports of the directional coupler. With feedback determined by the relative magnitude of optical power reflected by a FBG and the transmitted power, selective excitations of the LP01 and the LP11 modes are experimentally shown. As the final component of this thesis, we experimentally combine the AO-based mode control with time-division-multiplexing. By choosing reflected pulses with appropriate arrival time for mode control, we can selectively excite the LP11 mode at different FBG locations within the TMF, based on the ratio of optical signals reflected by FBGs in the TMF and the transmitted signal. Using two lasers set at the two FBG peak reflection wavelengths associated with the LP01 and the LP11 modes, we can accomplish AO-based mode control within a TMF by using only the reflection signals from the FBG. By using the ratio of the reflected signals of two lasers as feedback, we demonstrate selective excitation of almost pure LP01 or LP11 mode at the FBG location within the TMF. The method developed in this thesis is generic and can be extended to many other applications using appropriately chosen feedback signals. It is possible to generalize the AO-based mode control method to MMF as well. This method may find important applications in MMF-based communication, sensing and imaging et. al. in the future.
Aging processes in complex systems
Afzal, Nasrin (Virginia Tech, 2013-04-27)
Recent years have seen remarkable progress in our understanding of physical aging in nondisordered systems with slow, i.e. glassy-like dynamics. In many systems a single dynamical length L(t), that grows as a power-law of time t or, in much more complicated cases, as a logarithmic function of t, governs the dynamics out of equilibrium. In the aging or dynamical scaling regime, these systems are best characterized by two-times quantities, like dynamical correlation and response functions, that transform in a specific way under a dynamical scale transformation. The resulting dynamical scaling functions and the associated non-equilibrium exponents are often found to be universal and to depend only on some global features of the system under investigation. We discuss three different types of systems with simple and complex aging properties, namely reaction diffusion systems with a power growth law, driven diffusive systems with a logarithmic growth law, and a non-equilibrium polymer network that is supposed to capture important properties of the cytoskeleton of living cells. For the reaction diffusion systems, our study focuses on systems with reversible reaction diffusion and we study two-times functions in systems with power law growth. For the driven diffusive systems, we focus on the ABC model and a related domain model and measure two- times quantities in systems undergoing logarithmic growth. For the polymer network model, we explain in some detail its relationship with the cytoskeleton, an organelle that is responsible for the shape and locomotion of cells. Our study of this system sheds new light on the non- equilibrium relaxation properties of the cytoskeleton by investigating through a power law growth of a coarse grained length in our system.
Aluminum plasmonic nanostructures for improved absorption in organic photovoltaic devices
Kochergin, V.; Neely, L.; Jao, C. Y.; Robinson, Hans D. (AIP Publishing, 2011-03)
We model the absorption enhancement in organic photovoltaic devices induced by incorporating Al, Ag, and Au nanoparticles in the active layer. We find that Al nanoparticles should yield significantly greater enhancement than Ag or Au. This is because the much higher plasma frequency of Al ensures a better overlap between plasmon resonance and absorption band of organic semiconductors. Our predictions are verified experimentally by demonstrating enhanced absorbance in a poly(3-hexylthiophene-2,5-diyl): [6,6]-phenyl C61 butyric acid methyl ester layer with embedded functionalized Al nanoparticles. (C) 2011 American Institute of Physics. [doi:10.1063/1.3574091]
The Application of Thin Film Ionic Self-assembled Multilayer (ISAM) Nanostructures in Electromechanical Bending Actuators and Micro-fabricated Gas Chromatography (uGC) Devices
Wang, Dong (Virginia Tech, 2015-01-14)
Ionic self-assembled multilayer (ISAM) thin film nanostructures, including highly porous and conductive gold nanoparticles (GNP), and highly porous and thermally stable silica nanoparticles (SNP), were fabricated via the layer-by-layer (LbL) self-assembly technique. Their application in ionic polymer-metal composite (IPMC) electromechanical bending actuators and microfabricated gas chromatography (microGC) devices were investigated and significant performance improvements of these devices were achieved. IPMC bending actuators, consisting of an ionic electroactive polymer (iEAP) membrane as backbone, ionic liquids (IL) as electrolyte, and ISAM GNP thin film as porous electrode, were fabricated and investigated. The influences of humidity, conductive network composite (CNC), and IL uptake on the bending performance were examined and discussed. An equivalent circuit model to simulate both the electrical and mechanical responses was also proposed and experimentally verified. Moreover, IPMC actuators made from other newly synthesized iEAP membranes were fabricated and tested. Some of them showed promising performance that was comparable or even better as compared to the ones made from Nafion. LbL fabricated ISAM SNPs thin film coatings were also applied in the microGC devices including micro fabricated thermal preconcentrators (microTPC) and separation columns (microSC) as adsorbent and stationary phase materials, respectively. New fabrication approaches were developed to selectively coat uniform conformal ISAM SNP coatings in these devices with different 3D microstructures. Thus, functionalized microTPCs and microSCs showed good performance, which can be further improved by using the ISAM SNPs coating as a nanotemplate for modifying additional polymer adsorbents or as the anchor sites for incorporating functional molecules for targeting detection.
Construction of an Optical Quarter-Wave Stack Using the ISAM (Ionic Self-Assembled Multilayers) Technique
Papavasiliou, Kriton (Virginia Tech, 2010-07-09)
The purpose of this thesis is to make a broadband antireflection coating configuration known as a quarter-wave stack consisting of one layer of titania and of one layer of silica nanoparticles. We utilize much that is already known about silica nanoparticle deposition. The first objective of this thesis is deposition and characterization of titania nanoparticle films deposited on glass microscope slides by a technique known as Ionic Self-Assembled Multilayers or ISAM deposition. This technique takes advantage of the electrostatic attraction between oppositely charged materials and ideally results in a uniform nanoparticle film whose thickness and optical properties can be tightly controlled. Deposition of a quarter-wave stack based on ISAM deposition of silica and titania nanoparticles is significantly simpler and less expensive than alternative deposition methods. Initial attempts to deposit titania films were unsuccessful because of excess diffuse scattering due to inhomogeneities in the film. In order to reduce diffuse scattering, two approaches were considered. The first approach was to improve the deposition process itself by experimenting with different values of deposition parameters such as solution pH and solution molarity. The other approach focused on removing the large nanoparticle aggregates from the colloidal solutions of titania nanoparticles that were suspected to be responsible for rough film surfaces resulting in diffuse scattering. This approach was successful. In addition, evidence suggested that surface roughness contributed more to diffuse scattering than the bulk of the films. After minimizing diffuse scattering from titania nanoparticle films, we used known results from research on silica nanoparticle films to deposit quarter-wave stacks consisting of one layer of titania nanoparticles with high refractive index and one layer of silica nanoparticles with low refractive index. This contrast in refractive indices is a desirable characteristic of quarter-wave stacks. The thicknesses and refractive indices of the two layers in the quarter-wave stacks were measured by ellipsometry and compared to the nominal thicknesses of these layers. Finally, the reflectance was derived from a model of the quarter-wave stack and was compared to the measured reflectance. It was found that construction of a quarter-wave stack by ISAM is possible but that it will be necessary to acquire data from more experiments.
Development of an Optical Fiber Biosensor with Nanoscale Self-Assembled Affinity Layer
Zuo, Ziwei (Virginia Tech, 2014-01-29)
Optical sensor systems that integrate Long-Period-Gratings (LPG) as the detection arm have been proven to be highly sensitive and reliable in many applications. With increasing public recognition of threats from bacteria-induced diseases and their potential outbreak among densely populated communities, an intrinsic, low-cost biosensor device that can perform quick and precise identification of the infection type is in high demand to respond to such challenging situations and control the damage those diseases could possibly cause. This dissertation describes the development of a biosensor platform that utilizes polymer thin films, known as ionic self-assembled multilayer (ISAM) films, to be the sensitivity- enhancing medium between an LPG fiber and specific, recognition layer. With the aid of cross- linking reactions, monoclonal antibodies (IgG) or DNA probes are immobilized onto the surface of the ISAM-coated fiber, which form the core component of the biosensor. By immersing such biosensor fiber into a sample suspension, the immobilized antibody molecules will bind the specific antigen and capture the target cells or cell fragments onto the surface of the fiber sensor, resulting in increasing the average thickness of the fiber cladding and changing the refractive index of the cladding. This change occurring at the surface of the fiber results in a decrease of optical power emerging from the LPG section of the fiber. By comparing the transmitted optical power before and after applying the sample suspension, we are able to determine whether or not certain bacterial species have attached to the surface of the fiber, and as a consequence, we are able to determine whether or not the solution contains the targeted bacteria. This platform has the potential for detection of a wide range of bacteria types. In our study, we have primarily investigated the sensitivity and specificity of the biosensor to methicillin- resistant Staphlococcus aureus (MRSA). The data we obtained have shown a sensitive threshold at as low as 102 cfu/ml with pure culture samples. A typical MRSA antibody-based biosensor assay with MRSA sample at this concentration has shown optical power reduction of 21.78%. In a detailed study involving twenty-six bacterial strains possessing the PBP2a protein that enables antibiotic resistance and sixteen strains that do not, the biosensor system was able to correctly identify every sample in pure culture samples at concentration of 104 cfu/ml. Further studies have also been conducted on infected mouse tissues and clinical swab samples from human ears, noses, and skin, and in each case, the system was in full agreement with the results of standard culture tests. However, the system is not yet able to correctly distinguish MRSA and non-MRSA infections in clinical swab samples taken from infected patient wounds. It is proposed that nonspecific binding due to insufficient blocking methods is the key issue. Other bacterial strains, such as Brucella and Francisella tularensis have also been studied using a similar biosensor platform with DNA probes and antibodies, respectively, and the outcomes are also promising. The Brucella DNA biosensor is able to reflect the existence of 3 Brucella strains at 100 cfu/ml with an average of 12.2% signal reduction, while negative control samples at 106cfu/ml generate an average signal reduction of -2.1%. Similarly, the F. tularensis antibodies biosensor has shown a 25.6% signal reduction to LVS strain samples at 100 cfu/ml, while for negative control samples at the same concentration, it only produces a signal reduction of 0.05%. In general, this biosensor platform has demonstrated the potential of detecting a wide range of bacteria in a rapid and relatively inexpensive manner.
Effects of Thickness, Morphology and Molecular Structure of Donor and Acceptor Layers in Thermally Interdiffused Polymer Photovoltaics
Gopal, Anamika (Virginia Tech, 2007-04-10)
An in-depth study of concentration gradients in thermally-interdiffused polymer – fullerene photovoltaic devices, with a focus on thickness and heat treatments, is presented in this thesis. Device performance is improved from the bilayer by the creation of a concentration gradient of the donor and acceptor materials throughout the active layer of the device. Concentration gradients are expected to improve device performance by optimizing the charge transfer, transport and collection processes. This is achieved through heat-induced interdiffusion of the two materials at temperatures above the glass transition temperature of the polymer. Investigation of the poly(3-octylthiophene) (P3OT) – C₆₀ system show a three-fold improvement in the external quantum efficiencies (EQE) as compared with bilayer devices. Auger spectroscopy, combined with argon-ion beam milling, serves to record the concentration depth profile and identify concentration gradients in the device through detection of the sulfur in the P3OT backbone. Concentration gradients are optimized to yield the best devices through a thickness variation study conducted on the P3OT – C₆₀ system for fixed thermal interdiffusion conditions at 118 °C for 5 minutes. An optimum thickness of 40 to 60 nm is obtained for the two materials that yields the ideal morphology of a concentration gradient as recorded by Auger spectroscopy. For such devices, the concentration gradient is seen to extend through the device, ending in a thin layer of pure material at each electrode. A monochromatic power conversion efficiency of 2.05% is obtained for 5.3 mW/cm²⁺ illumination at 470 nm. A brief study is also presented to optimize the concentration gradient profile through variations of the thermal parameters. The dependence of the concentration gradient on the interdiffusion time and temperature is investigated. The merits of heat treatment on the crystallinity of P3OT and the overall device performance are also discussed. It is shown in some case that devices with annealed P3OT layers show almost twice the EQE as non-annealed P3OT layer devices. Potential alternatives for C₆₀ in interdiffused devices with P3OT have been presented. [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM), a well-investigated acceptor for blend devices, is studied as an acceptor in concentration gradient devices. A method for spin-coating uniform bilayers of P3OT and PCBM, without solution damage to either layer, is presented. A thermal variation study of the interdiffusion conditions on this system indicated higher interdiffusion temperatures and times are preferred for P3OT – PCBM systems. For interdiffusion at 150 °C for ten minutes, EQE values approaching 35 % at 500 nm are obtained. Auger spectroscopy studies on this system yielded the same conclusions about the concentration gradient device morphology that gives optimum device output. 1:1 and 1:2 blends of P3OT – PCBM are also studied. The influence of various thermal treatments on these devices is described. The endohedral fullerene Sc₃N@C₈₀ is introduced as a new acceptor material. The endohedral fullerene consists of Sc₃N cluster enclosed in a C₈₀ cage. An order of magnitude increase is seen in device performance upon sublimation of these molecules on a P3OT layer confirming its effectiveness as an acceptor. Preliminary studies done on this system indicated the need for greater thermal treatment to produce optimum concentration gradients. An in depth study for varying temperatures and times is presented. The best device performance was seen for interdiffusion at 160 °C for 25 minutes. The endohedral fullerene devices also show a long-term deterioration and so best result are presented from a set of devices fabricated within the same time period. The study of these three donor-acceptor systems confirms that the conclusions on the thickness dependence and device performance study conducted for the P3OT – C₆₀ system extend to other acceptors. A model of EQE for varying thicknesses based on absorption in the interdiffused concentration gradient regions is also presented. This model effectively highlights the influence of P3OT layer thickness on the trends observed in the EQE. It did not, however, reproduce the experimental thickness variation results for varying C₆₀ thicknesses. Incorporation of the effects of the electric field intensity distribution is expected to correct for this. Suggestions have been given on how this might be achieved.
Electron Transport via Single Molecule Magnets with Magnetic Anisotropy
Luo, Guangpu (Virginia Tech, 2019-02-07)
Single molecule magnets (SMMs) are molecules of mesoscopic scale which exhibit quantum properties such as quantum tunneling of magnetization, quantum interference, spin filtering effects, strong spin-phonon coupling and strong hyperfine Stark effects. These effects allow applications of SMMs to high-density information storage, molecular spintronics, and quantum information science. Therefore, SMMs are of interest to physicists, chemists, and engineers. Recently, experimental fabrication of individual SMMs within transistor set-ups have been achieved, offering a new method to examine magnetic properties of individual SMMs. In this thesis, two types of SMMs, specifically Eu2(C8H8)3 and Ni9Te6(PEt3)8, are theoretically investigated by simulating their electron transport properties within three-terminal transistor set-ups. An extended metal atom chain (EMAC) consists of a string of metallic atoms with organic ligands surrounding the string. EMACs are an important research field for nanoelectronics. Homometallic iron-based EMACs are especially attractive due to the high spin and large magnetic anisotropy of iron(II). We explore the exchange coupling of iron atoms in two EMACs: [Fe2(mes)2(dpa)2] and [Fe4(tpda)3Cl2]. Chapter 1 provides an introduction to SMMs, electron transport experiments via SMMs and an introduction to density functional theory (DFT). Chapter 2 presents a theoretical study of electron transport via Eu2(C8H8)3. This type of molecule is interesting since its magnetic anisotropy type changes with oxidation state. The unique magnetic properties lead to spin blockade effects at zero and low bias. In other words, the current through this molecule is completely suppressed until the bias voltage exceeds a certain value. Chapter 3 discusses a theoretical study of electron transport via Ni9Te6(PEt3)8. The magnetic anisotropy of this magnetic cluster has cubic symmetry, which is higher than most SMMs. With appropriate magnetic anisotropy parameters, in the presence of an external magnetic field, uncommon phenomena such as low-bias blockade effects, negative conductance and discontinuous conductance lines, are observed. In Chapter 2 and 3 DFT-calculated magnetic anisotropy parameters are used and electron transport properties are calculated by solving master equations at low temperature. Chapter 4 examines the exchange coupling between iron ions in EMACs [Fe2(mes)2(dpa)2] and [Fe4(tpda)3Cl2]. The exchange coupling constants are calculated by using the least-squares fitting method, based on the DFT-calculated energies from different spin configurations.
Enhancement of second-order non-linear optical susceptibilities in organic film materials using non-centrosymmetric nanoparticles
(United States Patent and Trademark Office, 2010-08-10)
A non-linear optical material comprising a plurality of non-centrosymmetric nanoparticles juxtaposed to non-linear optical (NLO) film at a localized surface Plasmon resonance (LSPR) of the nanoparticles. The LSPR is resonant at a wavelength of an incident light source, wherein a second-order non-linear susceptibility (χ(2)) of the NLO film with respect to the incident light is enhanced by the juxtaposition to the LSPR of the nanoparticles. The non-linear optical material lacks global inversion symmetry.
Entrainment of Bacterial Synthetic Oscillators using Proteolytic Queueing and Aperiodic Signaling
Hochendoner, Philip Louis (Virginia Tech, 2015-12-12)
The bulk of this thesis considers how biological rhythms (oscillators) can be made to synchronize their rhythms by virtue of coupling to an external signal. Such externally controlled synchronization, known as entrainment, is explored using a synthetic biology approach in E.~coli, where I have used rationally designed gene circuits as an experimental model. Two novel modes of entrainment are explored: entrainment by competition between components for degradation, and entrainment by a noisy (aperiodic) stimulus. Both of these modes of entrainment can be shown to strongly synchronize ensembles of synthetic gene oscillators, and thus, these modes of entrainment may be important to understand the appearance of synchrony in natural systems. In addition to the study of entrainment, this thesis contains a general background of relevant material, contributions to the biophysics of multisite proteases, and updated protocols for experimental procedures in microfluidics and microscopy.
Experiments on the Thermal, Electrical, and Plasmonic Properties of Nanostructured Materials
Myers, Kirby (Virginia Tech, 2018-06-29)
Nanofabrication techniques continue to advance and are rapidly becoming the primary route to enhancement for the electrical, thermal, and optical properties of materials. The work presented in this dissertation details fabrication and characterization techniques of thin films and nanoparticles for these purposes. The four primary areas of research presented here are thermoelectric enhancement through nanostructured thin films, an alternative frequency-domain thermoreflectance method for thin film thermal conductivity measurement, thermal rectification in nanodendritic porous silicon, and plasmonic enhancement in silver nanospheroids as a reverse photolithography technique. Nanostructured thermoelectrics have been proposed to greatly increase thermopower efficiency and to bring thermoelectrics to mainstream power generation and cooling applications. In our work, thermoelectric thin films of SbTe, BiTe, and PbTe grown by atomic layer deposition and electrochemical atomic layer deposition were characterized for enhanced performance over corresponding bulk materials. Seebeck coefficient measurements were performed at temperatures ranging from 77 K to 380 K. Atomic composition was verified by energy-dispersive X-ray spectroscopy and structures were imaged by scanning electron microscopy. All thin films measured were ultimately found to have a comparable or smaller Seebeck coefficient to corresponding materials made by conventional techniques, likely due to issues with the growth process. Frequency-domain thermoreflectance offers a minimally invasive optical pump-probe technique for measuring thermal conductivity. Like time-domain thermoreflectance, the version of frequency-domain thermoreflectance demonstrated here relies on a non-zero thermo-optic coefficient in the sample, but uses moderate cost continuous wave lasers modulated at kHz or MHz frequencies rather than a more expensive ultrafast laser system. The longer timescales of these frequency ranges enables this technique to take measurements of films with thicknesses ranging from 100 nm to 10 um, complimentary to time-domain thermoreflectance. This method differentiates itself from other frequency-domain methods in that it is also capable of simultaneous independent measurements of both the in plane and out of plane values of the thermal conductivity in anisotropic samples through relative reflective magnitude, rather than phase, measurements. We validated this alternate technique by measuring the thermal conductivity of Al2O3 and soda-lime and found agreement both with literature values and with separate measurements obtained with a conventional time-domain thermoreflectance setup. Thermal rectification has the potential to enhance microcircuit performance, improve thermoelectric efficiency, and enable the creation of thermal logic circuits. Passive thermal rectification has been proposed to occur in geometrically asymmetric nanostructures when heat conduction is dominated by ballistic phonons. Here, nanodendritic structures with branch widths of ~ 10 nm and lengths of ~ 20 nm connected to ~ 50 um long trunks were electrochemically etched from <111> silicon wafers. Thermal rectification measurements were performed at temperatures ranging from 80 K to 250 K by symmetric thermal conductivity measurements. No thermal rectification was ultimately found in these samples within the margin of thermal conductivity measurement error 1%. This result is consistent with another study which found thermal rectification with greater conduction in the direction opposite to what ballistic phonon heat conduction theories predicted. Plasmonic resonance concentrates incident photon energy and enables channeling of that energy into sub-wavelength volumes where it can be used for nanoscale applications. We demonstrated that surface plasmon polaritons induced in silver nanosphereoid films by 532 nm light defunctionalize previously photocleaved ligands adsorbed onto the films, to yield a reverse photolithographic technique. In this method, gold nanosphere conjugation were conjugated to a photocleaved ligand, however conjugation could be inhibited by exposing the cleaved ligand to 532 nm light and consequently yield a reversal technique. This defunctionalizion effect did not occur on gold films or nanoparticles conjugated with the ligand in IR spectroscopy, and was observed to have a reduced effect in silver films relative to silver nanospheroid film. As silver nanospheroid films and gold nanospheres of the size used in this study are known to have plasmon resonance in the green wavelengths, while gold and silver continuous films do not, this defunctionalization likely results from plasmonic effects.
High quality factor silica microspheres functionalized with self-assembled nanomaterials
Kandas, Ishac L. N.; Zhang, Baigang; Daengngam, Chalongrat; Ashry, Islam; Jao, Chih-Yu; Peng, Bo; Ozdemir, Sahin K.; Robinson, Hans D.; Heflin, James R.; Yang, Lan; Xu, Yong (Optical Society of America, 2013-09-01)
With extremely low material absorption and exceptional surface smoothness, silica-based optical resonators can achieve extremely high cavity quality (Q) factors. However, the intrinsic material limitations of silica (e. g., lack of second order nonlinearity) may limit the potential applications of silica-based high Q resonators. Here we report some results in utilizing layer-by-layer self-assembly to functionalize silica microspheres with nonlinear and plasmonic nanomaterials while maintaining Q factors as high as 10(7). We compare experimentally measured Q factors with theoretical estimates, and find good agreement. (C) 2013 Optical Society of America
Investigating the effect of charge hydration asymmetry and incorporating it in continuum solvation framework
Mukhopadhyay, Abhishek (Virginia Tech, 2015-03-17)
One of the essential requirements of biomolecular modeling is an accurate description of water as a solvent. The challenge is to make this description computationally facile -- reasonably fast, simple, robust and easy to incorporate into existing software packages, yet accurate. The most rigorous procedure to model the effect of aqueous solvent is to explicitly model every water molecule in the system. For many practical applications, this approach is computationally too intense, as the number of required water atoms is on an average at least one order of magnitude larger than the number of atoms of the molecule of interest. Implicit solvent models, in which solvent molecules are replaced by a continuous dielectric, have become a popular alternative to explicit solvent methods. However, implicit solvation models often lack various microscopic details which are crucial for accuracy. One such missing effect that is currently missing from popular implicit models is the so called effect of charge hydration asymmetry (CHA). The missing effect of charge hydration asymmetry -- the asymmetric response of water upon the sign of solute charge -- manifests a characteristic, strong dependence of solvation free energies on the sign of solute charge. Here, we incorporate this missing effect into the continuum solvation framework via the conceptually simplest Born equation and also in the generalized Born model. We identify the key electric multipole moments of model water molecules critical for the various degrees of CHA effect observed in studies based on molecular dynamics simulations using different rigid water models. We then use this gained insight to incorporate CHA first into the Born model, and then into the generalized Born model. The proposed framework significantly improves accuracy of the hydration free energy estimates tested on a comprehensive set of varied molecular solutes -- monovalent and divalent ions, small drug-like molecules, charged and uncharged amino acid dipeptides, and small proteins. We finally develop a methodology to resolve the issue with unacceptably large uncertainty that stems from a variety of fundamental and technical difficulties in experimental quantification of CHA from charged solutes. Using the proposed corrections in the continuum framework, we untangle the charge-asymmetric response of water from its symmetric response, and further circumvent the difficulties by extracting accurate estimate propensity of water to cause CHA from accurate experimental hydration free energies of neutral polar molecules. We show that the asymmetry in water's response is strong, about 50% of the symmetric response.
Irreversible adsorption of gold nanospheres on fiber optical tapers and microspheres
Yi, Jihaeng; Jao, Chih-Yu; Kandas, Ishac L. N.; Liu, Bo; Xu, Yong; Robinson, Hans D. (AIP Publishing, 2012-04-01)
We study the adsorption of gold nanospheres onto cylindrical and spherical glass surfaces from quiescent particle suspensions. The surfaces consist of tapers and microspheres fabricated from optical fibers and were coated with a polycation, enabling irreversible nanosphere adsorption. Our results fit well with theory, which predicts that particle adsorption rates depend strongly on surface geometry and can exceed the planar surface deposition rate by over two orders of magnitude when particle diffusion length is large compared to surface curvature. This is particularly important for plasmonic sensors and other devices fabricated by depositing nanoparticles from suspensions onto surfaces with non-trivial geometries. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3701730]
Launching low-energy surface plasmons in purple gold (AuAl2)
Samaimongkol, Panupon; Robinson, Hans D. (Springer, 2019-03-01)
We confirm that the unusual purple color of the intermetallic compound AuAl 2 is of a plasmonic origin by launching surface plasmons (SPs) in thin AuAl 2 films. We measure the SP dispersion relation and also use the films to measure the index of refraction of sucrose solutions using standard SP resonance sensing. We find that the SP energy in planar AuAl 2 is approximately 2.1 eV, about 0.4 eV lower than in gold, and the material is highly resistant to oxidation. This is close to what is expected from previously reported measurements of the dielectric function of AuAl 2 . On this basis, we predict that AuAl 2 nanoparticles will a have very strong, spectrally nearly uniform light absorbance about an order of magnitude greater than standard carbon black. Such particles may therefore find applications as obscurants or as an alternative to more complex light-absorbing gold structures in areas such as photothermal therapy or solar steam generation, or in plasmonic catalysis.
Lithography Using an Atomic Force Microscope and Ionic Self-assembled Multilayers
Abdel Salam Khalifa, Moataz Bellah Mohammed (Virginia Tech, 2015-03-06)
This thesis presents work done investigating methods for constructing patterns on the nanometer scale. Various methods of nanolithography using atomic force microscopes (AFMs) are investigated. The use of AFMs beyond their imaging capabilities is demonstrated in various experiments involving nanografting and surface electrochemical modification. The use of an AFM to manipulate a monolayer of thiols deposited on a gold substrate via nanografting is shown in our work to enable chemical modification of the surface of the substrate by varying the composition of the monolayer deposited on it. This leads to the selective deposition of various polymers on the patterned areas. Conditions for enhancing the selective deposition of the self-assembled polymers are studied. Such conditions include the types of polymers used and the pH of the polyelectrolyte solutions used for polymer deposition. Another method of nanolithography is investigated which involves the electrochemical modification of a monolayer of silanes deposited on a silicon substrate. By applying a potential difference and maintaining the humidity of the ambient environment at a certain level we manage to change the chemical properties of select areas of the silane monolayer and thus manage to establish selective deposition of polymers and gold nanoparticles on the patterned areas. Parameters involved in the patterning process using surface electrochemical modification, such as humidity levels, are investigated. The techniques established are then used to construct circuit elements such as wires.
Modeling of nucleation-based stochastic processes in cellular systems
Xu, Xiaohua (Virginia Tech, 2010-08-11)
Molecular cell biology has been an intensively studied interdisciplinary field with the rapid development of experimental techniques and fast upgrade of computational hardware and numerical tools. Recent technological developments have led to single-cell experiments which allow us to probe the role of stochasticity in cellular processes. Stochastic modeling of the corresponding processes is thus an essential ingredient for the understanding and interpretation of cellular systems of interest. In this thesis, we explore several nucleation-based stochastic cellular processes, i.e. Min protein oscillation in Escherichia coli, pausing phenomena in DNA transcription, and single-molecule enzyme kinetics. We focus on the key experimental results and build up stochastic models accordingly to provide quantitative insights to the underlying physical mechanisms for the corresponding biological processes. We utilize specific mathematical methods and computational algorithms to gain a better understanding and make predictions for further experimental explorations in the relevant fields.
Multi-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfaces
Magill, Brenden A.; Guo, Xi; Peck, Cheryl L.; Reyes, Roberto L.; See, Erich M.; Santos, Webster L.; Robinson, Hans D. (Royal Society of Chemistry, 2019-01-01)
We quantitatively investigate lithographic patterning of a thiol-anchored self-assembled monolayer (SAM) of photocleavable o-nitrobenzyl ligands on gold through a multi-photon absorption process at 1.7 eV (730 nm wavelength). The photocleaving rate increases faster than the square of the incident light intensity, indicating a process more complex than simple two-photon absorption. We tentatively ascribe this observation to two-photon absorption that triggers the formation of a long-lived intermediate aci-nitro species whose decomposition yield is partially determined either by absorption of additional photons or by a local temperature that is elevated by the incident light. At the highest light intensities, thermal processes compete with photoactivation and lead to damage of the SAM. The threshold is high enough that this destructive process can largely be avoided, even while power densities are kept sufficiently large that complete photoactivation takes place on time scales of tens of seconds to a few minutes. This means that this type of ligand can be activated at visible and near infrared wavelengths where plasmonic resonances can easily be engineered in metal nanostructures, even though their single-photon reactivity at these wavelengths is negligible. This will allow selective functionalization of plasmon hotspots, which in addition to high resolution lithographic applications would be of benefit to applications such as Surface Enhanced Raman Spectroscopy and plasmonic photocatalysis as well as directed bottom-up nanoassembly.
Nonequilibrium Relaxation and Aging Scaling Properties of the Coulomb Glass and Bose Glass
Shimer, Matthew Timothy (Virginia Tech, 2011-08-26)
We use Monte Carlo simulations in order to investigate the density of states and the two-time density autocorrelation function for the two- and three-dimensional Coulomb glass as well as the Bose glass phase of flux lines in type-II superconductors. We find a very fast forming gap in the density of states and explore the dependence of temperature and filling fraction. By studying two scaling methods, we find that the nonequilibrium relaxation properties can be described sufficiently by a full-aging scaling analysis. The scaling exponents depend on both temperature and filling fraction, and are thus non-universal. We look at the trends of these exponents and found that as either the temperature decreases or the filling fraction deviates more from half-filling, the exponents reflect slower relaxation kinetics. With two separate interaction potentials, a comparison of relaxation rates and the gap in the density of states is made.
Optical Fiber Microstructures for Self-Contained Whispering Gallery Mode Excitation
Fraser, Michael John (Virginia Tech, 2016-05-02)
Optical resonators, which confine light by resonant recirculation, serve as the basis for a wide variety of optical components. Though they appear in many geometric forms, the most effective of optical resonators show axial symmetry in at least one dimension. A popular variation that finds broad application is the dielectric sphere. Acclaimed for their high quality (Q) factor and small modal volume, spheres owe credit of these attractive features to their support of whispering gallery mode (WGM) resonances. The sensitivity of a resonance's frequency and Q to strain, temperature, and other parameters of the surrounding medium can be the basis for ultracompact modulators and sensors. Physically, WGMs are special optical modes which can be understood as light rays that orbit the equator of the sphere guided by total internal reflection. Like a smooth stone can be skipped along the surface of a pond, light can be confined to the inside of a sphere by successive reflections. To best excite WGMs, the source light should initially trace a line tangent to the sphere's circumference. But incorporating a tiny sphere with such nanometric tolerances into a practical sensor structure has its challenges and the prospects for microsphere applications have suffered because of the plight of this problem. The work in this dissertation details the fabrication and function of three new "press fit" spherical resonators. These etched fiber micro-devices were developed to meet the demand for a robust, self-integrated means of coupling light between an optical fiber and WGMs in a microsphere resonator. The etching processes have been tuned to enable secure storage of a microsphere while also providing efficient excitation and interrogation of WGMs. Furthermore, the methods have been designed to be staightforward, quick, and repeatable. Using standard etchants on common polarization-maintaining fiber with readily purchased microspheres, the press fit resonators demonstrated here can be batch-fabricated and assembled. The press fit spherical resonator offers an alignment-free and conveniently pigtailed WGM coupler that has great potential for bio-science sensing applications and studies of resonant bispheres.

Browsing by Author "Robinson, Hans D."

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